Coloring matter, ink, ink for ink jet, ink jet recording method, color toner, and color filter

ABSTRACT

[Problem] To provide a coloring matter which has a good hue, and is capable of forming an image high in fastness property under various use conditions and environmental conditions, and particularly suitable for an ink. 
     [Solving Means] A coloring matter represented by the following formula (I): 
     
       
         
         
             
             
         
       
         
         
           
             wherein in the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3; when n is 1, R, X, Y, Z, Q, and G each represents a monovalent group; when n is 2, R, X, Y, Z, Q, and G each represents a monovalent or divalent substituent, provided that at least one represents a divalent substituent; and when n is 3, R, X, Y, Z, Q, and G each represents a monovalent, divalent or trivalent substituent, provided that at least two each represents a divalent substituent, or at least one represents a trivalent substituent.

This application is a divisional of U.S. patent application Ser. No.11/795,581 filed Jul. 19, 2007, which is a national stage of PCTApplication No. PCT/JP2005/014439 filed Aug. 5, 2005, which claimsbenefit to Japanese Patent Application No. 2005-030466 filed Feb. 7,2005, and Japanese Patent Application No. 2005-226768 filed Aug. 4,2005. The above-noted applications are incorporated herein by referencein their entirety.

TECHNICAL FIELD

The present invention relates to an ink, an ink for ink jet, an ink jetrecording method, a method for improving the weatherability of a formedcolored image material, an ink sheet, a color toner, and a color filter.

BACKGROUND ART

In recent years, as image recording materials, particularly, materialsfor forming color images have been mainstream. Specifically, recordingmaterials of an ink jet system, recording materials of a heat sensitivetransfer system, recording materials of an electrophotographic system,transfer type silver halide light sensitive materials, printing inks,recording pens, and the like have found widespread use. Whereas, inimage pickup devices such as CCDs for photographing equipment, and inLCDs and PDPs for displays, color filters are used forrecording/reproducing color images. For these color image recordingmaterials and color filters, coloring matters (dyes and pigments) ofthree primary colors of a so-called additive color mixing process orsubtractive color mixing process have been used in order to display orrecord full-color images. However, in actuality, there is no fastcoloring matter having the absorption characteristics capable ofrealizing a preferred color reproduction region, and resisting varioususe conditions and environmental conditions. Thus, the improvementthereof has been strongly desired.

The coloring matters for use in the respective applications are requiredto have in common the following properties. Namely, the absorptioncharacteristics in terms of color reproduction are preferable; fastnessproperties under the environmental conditions in which they are used,such as the light resistance, heat resistance, moisture resistance, theresistance to an oxidizing gas such as ozone, fastness properties tochemicals such as sulfurous acid gas are good; the storage stability inan ink is excellent; and other properties. There is a strong demand fora coloring matter which has a good yellow hue, is fast to light, moistheat, and active gases in the environment, and is excellent in storagestability.

As the coloring matter skeleton of yellow for use as an ink for ink jet,azo type one is typical. As the typical azo coloring matter, inJP-A-2003-277662, there is described a fast coloring matter having atriazinyl pyrazole skeleton. However, there is further a demand for acoloring matter excellent in storage stability in an ink.

Patent Document 1:JP-A-2003-277662

DISCLOSURE OF THE INVENTION Problems that the Invention is to Solve

It is objects of the present invention to resolve the problems in therelated art, and to attain the following objects.

Namely, the objects of the invention are 1) to provide a coloring matterwhich has the absorption characteristics of excellent color reproductionas the coloring matter of three primary colors, has sufficient fastnessproperties to light, heat, moisture, and active gases in theenvironment, and excellent in the storage stability in an ink; 2) toprovide various coloring compositions (inks) for an ink for ink jetprinting or other printing, an ink sheet in a heat sensitive recordingmaterial, a color toner for electrophotography, and a color filter foruse in a display such as LCD or PDP, or an image pick-up device such asCCD, for providing a colored image or a colored material excellent inhue and fastness properties, and 3) to provide, particularly, an ink forink jet recording which is excellent in storage stability in an ink, hasa good hue, and is capable of forming an image high in fastnessproperties to light, moist heat, and active gases in the environment,particularly, an ozone gas, and an ink jet recording method.

Means for Solving the Problems

The present inventors conducted a close study on a pyrazolyl azocoloring matter derivative aiming at a coloring matter excellent in inkstability, having a good hue, and high in fastness properties to light,ozone, and moist heat. As a result, they found that the problems can besolved by the compounds represented by the following formulae (I), and(1) to (6), leading to the completion of the invention. The means forsolving the problems are as follows.

<1> A coloring matter represented by the following formula (I):

wherein in the formula, G represents a heterocyclic group, and nrepresents an integer of 1 to 3; when n is 1, R, X, Y, Z, Q, and G eachrepresents a monovalent group; when n is 2, R, X, Y, Z, Q, and G eachrepresents a monovalent or divalent substituent, provided that at leastone represents a divalent substituent; and when n is 3, R, X, Y, Z, Q,and G each represents a monovalent, divalent, or trivalent substituent,provided that at least two each represents a divalent substituent, or atleast one represents a trivalent substituent.

<2> The coloring matter represented by the following formula (1),formula (2), formula (3), formula (4), or formula (5):

wherein in the formula, R₁, R₂, X₁, X₂, Y₁, Y₂, Z₁, and Z₂ eachrepresents a monovalent group, G represents an atomic group forming a 5-to 8-membered nitrogen-containing heterocyclic ring, and M represents ahydrogen atom or a cation;

wherein in the formula, R₁, R₂, R₁₁, R₁₂, X₁, X₂, Z₁, and Z₂ eachrepresents a monovalent group, L₁ represents a divalent linking group,G₁ and G₂ each independently represents an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring, and M represents ahydrogen atom or a cation;

wherein in the formula, R₁, R₂, R₁₁, R₁₂, X₁, X₂, Y₁, and Y₂ eachrepresents a monovalent group, L₂ represents a divalent linking group,G₁ and G₂ each independently represents an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring, and M represents ahydrogen atom or a cation;

wherein in the formula, R₁₁, R₁₂, X₁, X₂, Y₁, Y₂, Z₁, and Z₂ eachrepresents a monovalent group, L₃ represents a divalent linking group,G₁ and G₂ each independently represents an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring, and M represents ahydrogen atom or a cation; and

wherein in the formula, R₁, R₂, R₁₁, R₁₂, Y₁, Y₂, Z₁, and Z₂ eachrepresents a monovalent group, L₄ represents a divalent linking group,G₁ and G₂ each independently represents an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring, and M represents ahydrogen atom or a cation.

<3> The coloring matter according to the item <2>,

wherein each nitrogen-containing heterocyclic ring represented by G, G₁,and G₂ in the formula (1), the formula (2), the formula (3), the formula(4), and the formula (5) is a S-triazine ring.

<4> The coloring matter according to the item <2>,

wherein the coloring matter represented by the formula (1) is a coloringmatter represented by the following formula (6):

where in the formula, R₁, R₂, Y₁, and Y₂ each represents a monovalentgroup; X₁ and X₂ each independently represents an electron attractinggroup with a Hammett's σp value of 0.20 or more; Z₁ and Z₂ eachindependently represents a hydrogen atom, a substituted or unsubstitutedalkyl group, a substituted or unsubstituted alkenyl group, a substitutedor unsubstituted alkynyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, or a substituted orunsubstituted heterocyclic group; and M represents a hydrogen atom or acation.

<5> An ink comprising at least one coloring matter according to any ofthe items <1> to <4>.

<6> An ink for ink jet recording which uses an ink according to the item<5>.

<7> An ink jet recording method for image formation using an inkaccording to the item <6>.

<8> An ink jet recording method comprising:

forming an image on an image receiving material having an ink imagereceiving layer containing white inorganic pigment particles on asupport using an ink according to the item <6>.

<9> A method for improving weatherability of a colored image materialformed by using an ink according to the item <6>.

<10> An ink sheet comprising at least one coloring matter according toany of the items <1> to <4>.

<11> A color toner comprising at least one coloring matter according toany of the items <1> to <4>.

<12> A color filter comprising at least one coloring matter according toany of the items <1> to <4>.

<13> A compound represented by the following formula (7), or a salt or ahydrate thereof:

wherein in the formula, R₃ and R₄ each independently represents amonovalent group; P₁ and P₂ each independently represents a hydrogenatom or a leaving group; and M represents a hydrogen atom or a cation.

Advantage of the Invention

The coloring matter of the present invention is excellent in storagestability in an ink. It has the absorption characteristics of excellentcolor reproduction as the coloring matter of three primary colors, andhas sufficient fastness properties to light, heat, moisture, and activegases in the environment. Further, the coloring matter is suitable asfor various coloring compositions of an ink for ink jet printing orother printing, an ink sheet in a heat sensitive recording material, acolor toner for electrophotography, and a color filter for use in adisplay such as LCD or PDP, or an image pick-up device such as CCD, forproviding a colored image or a colored material excellent in hue andfastness properties. Particularly, use of the coloring matter canprovide an ink for ink jet recording which is excellent in storagestability in an ink, has a good hue, and is capable of forming an imagehigh in fastness properties to light, and active gases in theenvironment, particularly, an ozone gas, and an ink jet recordingmethod.

BEST MODE FOR CARRYING OUT THE INVENTION

Below, the present invention will be described in details.

[Azo Coloring Matter]

Herein, the Hammett's substituent constant σup value used in thisspecification will be explained to some extent. The Hammett's rule is anempirical rule proposed by L. P. Hammett in 1935 in order to discussquantitatively the effect of a substituent on the reaction orequilibrium of benzene derivatives. The propriety of the rule is widelyrecognized at present. The substituent constants determined by theHammett's rule include the σp value and the σm value. These values canbe found widely in common literature. For example, these arespecifically described in Lange's Handbook of Chemistry, 12th Edition,compiled by J. A. Dean, 1979, (McGraw Hill), and Kagaku No Ryouiki, aspecial issue, No. 122, pp. 96 to 103, 1979, (Nankoudo). Incidentally,although in the invention, respective substituents are defined by theHammett's substituent constant σp value, or described thereby, thisshould not be construed as limitation to only substituents whose valuesare known by literature and can be found in the above publications, andshould naturally be construed as including substituents whose values,even if unknown by literature, would be included in the ranges whenmeasured according to the Hammett's rule. Although the compoundsrepresented by the formula (B) of the invention are not benzenederivatives, the σp value is used, irrespective of substitution site, asa scale for showing the electronic effect of substituents thereof. Inthe invention, the σp value will be hereinafter used in such a meaning.

The azo coloring matters in the invention are the azo coloring mattersrepresented by the formulae (1) to (6).

Below, the formula (I) will be described in details.

where in the formula, G represents a heterocyclic group, and nrepresents an integer of 1 to 3.

When n is 1, R, X, Y, Z, Q, and G each represent a monovalent group, andrepresent a monoazo coloring matter represented by the formula in theparentheses.

When n is 2, R, X, Y, Z, Q, and G each represent a monovalent ordivalent group, provided that at least one represents a divalentsubstituent, and represent a bis type azo coloring matter of thecoloring matter represented by the formula in the parentheses.

When n is 3, R, X, Y, Z, Q, and G each represent a divalent or trivalentgroup, provided that at least two each represent a divalent substituent,or at least one represents a trivalent substituent, and represent a tristype azo coloring matter of the coloring matter represented by theformula in the parentheses.

Below, the formula (I) will be further described in details.

In the formula (I), preferred examples of the substituent of G includepreferably 5- to 8-membered heterocyclic groups. Out of these, 5- to8-membered substituted or unsubstituted, aromatic or nonaromaticheterocyclic groups are preferred. They may be further condensed. A 5-or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms isfurther preferred.

Examples of the heterocyclic group represented by the G may include,with no limitation on substitution site, pyridine, pyrazine, pyridazine,pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline,phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene,benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole,benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole,thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine,piperazine, imidazolidine, and thiazoline.

When the heterocyclic group is a group capable of further having asubstituent, it may further have the following substituents.

Mention may be made of a straight chain or branched alkyl group having 1to 12 carbon atoms, a straight chain or branched aralkyl group having 7to 18 carbon atoms, a straight chain or branched alkenyl group having 2to 12 carbon atoms, a straight chain or branched alkynyl group having 2to 12 carbon atoms, a straight chain or branched cycloalkyl group having3 to 12 carbon atoms, a straight-chain or branched cycloalkenyl grouphaving 3 to 12 carbon atoms (out of the foregoing respective groups,those having branched chains are preferable because they improve thesolubility of the dye and the stability of the ink; and those havingasymmetric carbons are particularly preferred; examples of which includemethyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl,2-methyl sulfonyl ethyl, 3-phenoxypropyl, trifluoromethyl, andcyclopentyl), a halogen atom (e.g., a chlorine atom or a bromine atom),an aryl group (e.g., phenyl, 4-t-butylphenyl, or 2,4-di-t-amyl phenyl),a heterocyclic group (e.g., imidazolyl, pyrazolyl, thoriazolyl, 2-furyl,2-thienyl, 2-pyrimidinyl, or 2-benzothiazolyl), a cyano group, ahydroxyl group, a nitro group, a carboxy group, an amino group, analkyloxy group (e.g., methoxy, ethoxy, 2-methoxyethoxy, or 2-methylsulfonyl ethoxy), an aryloxy group (e.g., a phenoxy, 2-methyl phenoxy,4-t-butyl phenoxy, 3-nitro phenoxy, 3-t-butyloxy carbonyl phenoxy, or3-methoxy carbonylphenyloxy), or an acylamino group (e.g., acetamide,benzamide, or 4-(3-t-butyl-4-hydroxy phenoxy)butane amide), analkylamino group (e.g., methylamino, butylamino, diethylamino, or methylbutylamino), an anilino group (e.g., phenyl amino or 2-chloroanilino),an ureido group (e.g., phenylureido, methylureido, orN,N-dibutylureido), a sulfamoyl amino group (e.g., N,N-dipropylsulfamoyl amino), an alkyl thio group (e.g., methyl thio, octyl thio,2-phenoxyethyl thio), an aryl thio group (e.g., phenyl thio,2-butoxy-5-t-octylphenyl thio, or 2-carboxy phenyl thio), an alkyloxycarbonyl amino group (e.g., methoxy carbonyl amino), an alkyl sulfonylamino group, and an aryl sulfonyl amino group (e.g., methyl sulfonylamino, phenyl sulfonyl amino, or p-toluene sulfonyl amino), a carbamoylgroup (e.g., N-ethyl carbamoyl or N,N-dibutyl carbamoyl), a sulfamoylgroup (e.g., N-ethyl sulfamoyl, N,N-dipropyl sulfamoyl, or N-phenylsulfamoyl), a sulfonyl group (e.g., methyl sulfonyl, octyl sulfonyl,phenyl sulfonyl, or p-toluene sulfonyl), an alkyloxy carbonyl group(e.g., methoxy carbonyl or butyloxy carbonyl), a heterocyclic oxy group(e.g., 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group(e.g., phenylazo, 4-methoxyphenyl azo, 4-pivaloylamino phenylazo,2-hydroxy-4-propanoyl phenylazo), an acyloxy group (e.g., acetoxy), acarbamoyloxy group (e.g., N-methyl carbamoyloxy orN-phenylcarbamoyloxy), a silyloxy group (e.g., trimethyl silyloxy ordibutyl methyl silyloxy), an aryloxy carbonyl amino group (e.g., phenoxycarbonyl amino), an imido group (e.g., N-succinimido or N-phthalimido),a heterocyclic thio group (e.g., 2-benzothiazolyl thio,2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group(e.g., 3-phenoxypropyl sulfinyl), a phosphonyl group (e.g., phenoxyphosphonyl, octyloxy phosphonyl, or phenyl phosphonyl), an aryloxycarbonyl group (e.g., phenoxy carbonyl), an acyl group (e.g., acetyl,3-phenyl propanoyl, or benzoyl), and ionic hydrophilic groups (e.g., acarboxyl group, a sulfo group, phosphono group, and a quaternaryammonium group).

Preferred examples of the substituents of Q, R, X, Y, and Z in theformula (I) will be described in details.

When Q, R, X, Y, and Z each represent a monovalent group, they eachrepresent a hydrogen atom or a monovalent substituent as a monovalentgroup. The monovalent substituent will be described in more details.Examples of the monovalent substituent may include a halogen atom, analkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, analkynyl group, an aryl group, a heterocyclic group, a cyano group, ahydroxyl group, a nitro group, an alkoxy group, an aryloxy group, asilyloxy group, a heterocyclic oxy group, an acyloxy group, acarbamoyloxy group, an alkoxy carbonyloxy group, an aryloxy carbonyloxygroup, an amino group (an alkylamino group or an arylamino group), anacylamino group (amido group), an amino carbonyl amino group (an ureidogroup), an alkoxy carbonyl amino group, an aryloxy carbonyl amino group,a sulfamoyl amino group, an alkyl sulfonyl amino group, an aryl sulfonylamino group, an alkyl thio group, an aryl thio group, a heterocyclicthio group, a sulfamoyl group, an alkyl sulfinyl group, an aryl sulfinylgroup, an alkyl sulfonyl group, an aryl sulfonyl group, an acyl group,an aryloxy carbonyl group, an alkoxy carbonyl group, a carbamoyl group,a phosphino group, a phosphinyl group, a phosphinyloxy group, aphosphinyl amino group, a silyl group, an azo group, or an imido group.Each may further have a substituent.

Out of these, particularly preferred is a hydrogen atom, a halogen atom,an alkyl group, an aryl group, a heterocyclic group, a cyano group, analkoxy group, an amido group, an ureido group, an alkyl sulfonyl aminogroup, an aryl sulfonyl amino group, a sulfamoyl group, an alkylsulfonyl group, an aryl sulfonyl group, a carbamoyl group, or an alkoxycarbonyl group. Particularly, a hydrogen atom, a halogen atom, an alkylgroup, an aryl group, a cyano group, an alkyl sulfonyl group, an arylsulfonyl group, or a heterocyclic group is preferred. A hydrogen atom,an alkyl group, an aryl group, a cyano group, or an alkyl sulfonyl groupis most preferred.

Below, the Q, R, X, Y, and Z will be further described in more details.

The halogen atoms represented by Q, R, X, Y, and Z each represent achlorine atom, a bromine atom, or an iodine atom. Out of these, achlorine atom or a bromine atom is preferred. Particularly, a chlorineatom is preferred.

The alkyl groups represented by Q, R, X, Y, and Z include a substitutedor unsubstituted alkyl group. The substituted or unsubstituted alkylgroup is preferably an alkyl group having 1 to 30 carbon atoms. As theexamples of the substituent, mention may be made of the same ones as thesubstituents as mentioned when the G is a group capable of furtherhaving a substituent. Out of these, a hydroxy group, an alkoxy group, acyano group, and a halogen atom, a sulfo group (which may also be in theform of a salt) or a carboxyl group (which may also be in the form of asalt) is preferred. Examples of the alkyl group may include methyl,ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl,cyano ethyl, or 4-sulfobutyl.

The cycloalkyl groups represented by Q, R, X, Y, and Z include asubstituted or unsubstituted cycloalkyl group. The substituted orunsubstituted cycloalkyl group is preferably a cycloalkyl group having 5to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of thecycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

The aralkyl groups represented by Q, R, X, Y, and Z include asubstituted or unsubstituted aralkyl group. The substituted orunsubstituted aralkyl group is preferably an aralkyl group having 7 to30 carbon atoms. As the examples of the substituent, mention may be madeof the same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the aralkyl mayinclude benzyl and 2-phenethyl.

The alkenyl groups represented by Q, R, X, Y, and Z include astraight-chain, branched, or cyclic substituted or unsubstituted alkenylgroup. It is preferably a substituted or unsubstituted alkenyl grouphaving 2 to 30 carbon atoms, examples of which may include vinyl, allyl,prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, and 2-cyclohexen-1-yl.

The alkynyl groups represented by Q, R, X, Y, and Z are each asubstituted or unsubstituted alkynyl group having 2 to 30 carbon atoms.Examples thereof may include ethynyl or propargyl.

The aryl groups represented by Q, R, X, Y, and Z are each a substitutedor unsubstituted aryl group having 6 to 30 carbon atoms. Examplesthereof may include phenyl, p-tolyl, naphthyl, m-chlorophenyl, oro-hexadecanoyl aminophenyl. As the examples of the substituent, mentionmay be made of the same ones as the substituents as mentioned when the Gis a group capable of further having a substituent.

The heterocyclic groups represented by Q, R, X, Y, and Z are each amonovalent group obtained by removing one hydrogen atoms from a 5- or6-membered substituted or unsubstituted, aromatic or nonaromaticheterocyclic compound, which may also be further condensed. It isfurther preferably a 5- or 6-membered aromatic heterocyclic group having3 to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of theheterocyclic group may include, with no limitation on substitution site,pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline,isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole,indole, furan, benzofuran, thiophene, benzothiophene, pyrazole,imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole,benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole,benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, andthiazoline.

The alkoxy groups represented by Q, R, X, Y, and Z each include asubstituted or unsubstituted alkoxy group. The substituted orunsubstituted alkoxy group is preferably an alkoxy group having 1 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the alkoxy groupmay include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy,hydroxyethoxy, and 3-carboxy propoxy.

The aryloxy groups represented by Q, R, X, Y, and Z are each preferablya substituted or unsubstituted aryloxy group having 6 to 30 carbonatoms. As the examples of the substituent, mention may be made of thesame ones as the substituents as mentioned when the G is a group capableof further having a substituent. Examples of the aryloxy group mayinclude phenoxy, 2-methyl phenoxy, 4-t-butyl phenoxy, 3-nitro phenoxy,and 2-tetradecanoyl amino phenoxy.

The silyloxy groups represented by Q, R, X, Y, and Z are each preferablya silyloxy group having 3 to 20 carbon atoms. Examples thereof mayinclude trimethyl silyloxy and t-butyldimethyl silyloxy.

The heterocyclic oxy groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted heterocyclic oxy group having2 to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of theheterocyclic oxy group may include, for example, 1-phenyltetrazol-5-oxy,and 2-tetrahydorpyranyloxy.

The acyloxy groups represented by Q, R, X, Y, and Z are each preferablya formyloxy group, a substituted or unsubstituted alkyl carbonyloxygroup having 2 to 30 carbon atoms, or a substituted or unsubstitutedaryl carbonyloxy group having 6 to 30 carbon atoms. As the examples ofthe substituent, mention may be made of the same ones as thesubstituents as mentioned when the G is a group capable of furtherhaving a substituent. Examples of the acyloxy group may include, forexample, formyloxy, acetyloxy, pivaloyloxy, steaaroyloxy, benzoyloxy,and p-methoxyphenyl carbonyloxy.

The carbamoyloxy groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted carbamoyloxy group having 1 to30 carbon atoms. As the examples of the substituent, mention may be madeof the same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the carbamoyloxygroup may include, for example, N,N-dimethyl carbamoyloxy, N,N-diethylcarbamoyloxy, morpholino carbonyloxy, and N,N-di-n-octyl aminocarbonyloxy, N-n-octyl carbamoyloxy.

The alkoxy carbonyloxy groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted alkoxy carbonyloxy grouphaving 2 to 30 carbon atoms. As the examples of the substituent, mentionmay be made of the same ones as the substituents as mentioned when the Gis a group capable of further having a substituent. Examples of thealkoxy carbonyloxy group may include, for example, methoxy carbonyloxy,ethoxy carbonyloxy, t-butoxy carbonyloxy, and n-octyl carbonyloxy.

The aryloxy carbonyloxy groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted aryloxy carbonyloxy grouphaving 7 to 30 carbon atoms. As the examples of the substituent, mentionmay be made of the same ones as the substituents as mentioned when the Gis a group capable of further having a substituent. Examples of thearyloxy carbonyloxy group may include, for example, phenoxy carbonyloxy,p-methoxyphenoxy carbonyloxy, and p-n-hexadecyloxy phenoxy carbonyloxy.

The amino groups represented by Q, R, X, Y, and Z are each preferably asubstituted or unsubstituted alkylamino group having 1 to 30 carbonatoms, a substituted or unsubstituted arylamino group having 6 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the amino group mayinclude, for example, amino, methylamino, dimethylamino, anilino,N-methyl-anilino, diphenyl amino, hydroxyethylamino, carboxyethylamino,sulfoethylamino, and 3,5-dicarboxy anilino.

The acylamino groups represented by Q, R, X, Y, and Z are eachpreferably a formyl amino group, a substituted or unsubstituted alkylcarbonyl amino group having 1 to 30 carbon atoms, or a substituted orunsubstituted aryl carbonyl amino group having 6 to 30 carbon atoms. Asthe examples of the substituent, mention may be made of the same ones asthe substituents as mentioned when the G is a group capable of furtherhaving a substituent. Examples of the acylamino group may include, forexample, formylamino, acetylamino, pivaloylamino, lauroylamino,bonzoylamino, and 3,4,5-tri-n-octyloxyphenyl carbonyl amino.

The amino carbonyl amino groups represented by Q, R, X, Y, and Z areeach preferably a substituted or unsubstituted amino carbonyl aminogroup having 1 to 30 carbon atoms. As the examples of the substituent,mention may be made of the same ones as the substituents as mentionedwhen the G is a group capable of further having a substituent. Examplesof the amino carbonyl amino group may include, for example,carbamoylamino, N,N-dimethylamino carbonyl amino, N,N-diethylaminocarbonyl amino, and morpholino carbonyl amino.

The alkoxy carbonyl amino groups represented by Q, R, X, Y, and Z areeach preferably a substituted or unsubstituted alkoxy carbonyl aminogroup having 2 to 30 carbon atoms. As the examples of the substituent,mention may be made of the same ones as the substituents as mentionedwhen the G is a group capable of further having a substituent. Examplesof the alkoxy carbonyl amino group may include, for example, methoxycarbonyl amino, ethoxy carbonyl amino, t-butoxy carbonyl amino,N-octadecyloxy carbonyl amino, and N-methyl-methoxy carbonyl amino.

The aryloxy carbonyl amino groups represented by Q, R, X, Y, and Z areeach preferably a substituted or unsubstituted aryloxy carbonyl aminogroup having 7 to 30 carbon atoms. As the examples of the substituent,mention may be made of the same ones as the substituents as mentionedwhen the G is a group capable of further having a substituent. Examplesof the aryloxy carbonyl amino group may include, for example, phenoxycarbonyl amino, p-chlorophenoxy carbonyl amino, and m-n-octyloxy phenoxycarbonyl amino.

The sulfamoyl amino groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted sulfamoyl amino group having 0to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of the sulfamoylamino groups may include, for example, sulfamoyl amino,N,N-dimethylamino sulfonyl amino, N-n-octylamino sulfonylamino.

The alkyl and aryl sulfonyl amino groups represented by Q, R, X, Y, andZ are each preferably a substituted or unsubstituted alkyl sulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstitutedaryl sulfonyl amino group having 6 to 30 carbon atoms amino group. Asthe examples of the substituent, mention may be made of the same ones asthe substituents as mentioned when the G is a group capable of furtherhaving a substituent. Examples of the alkyl sulfonyl amino group andaryl sulfonyl amino group may include, for example, methyl sulfonylamino, butyl sulfonyl amino, phenyl sulfonyl amino,2,3,5-trichlorophenyl sulfonyl amino, and p-methyl phenyl sulfonylamino.

The alkyl thio groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted alkyl thio group having 1 to30 carbon atoms. As the examples of the substituent, mention may be madeof the same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the alkyl thiogroup may include, for example, methyl thio, ethyl thio, and n-hexadecylthio.

The aryl thio groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted aryl thio group having 6 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the aryl thiogroups may include, for example, phenyl thio, p-chlorophenyl thio, andm-methoxyphenyl thio.

The heterocyclic thio groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted heterocyclic thio group having2 to 30. As the examples of the substituent, mention may be made of thesame ones as the substituents as mentioned when the G is a group capableof further having a substituent. Examples of the heterocyclic thiogroups may include, for example, 2-benzothiazolyl thio, and1-phenyltetrazol-5 -ylthio.

The sulfamoyl groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted sulfamoyl group having 0 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the sulfamoylgroups may include, for example, N-ethyl sulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethyl sulfamoyl, N-acetyl sulfamoyl, N-benzoylsulfamoyl, and N-(N′-phenyl carbamoyl)sulfamoyl).

The alkyl and aryl sulfinyl groups represented by Q, R, X, Y, and Z areeach preferably a substituted or unsubstituted alkyl sulfinyl grouphaving 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. As the examples of thesubstituent, mention may be made of the same ones as the substituents asmentioned when the G is a group capable of further having a substituent.Examples of the alkyl and aryl sulfinyl groups may include, for example,methyl sulfinyl, ethyl sulfinyl, phenyl sulfinyl, and p-methyl phenylsulfinyl.

The alkyl and aryl sulfonyl groups represented by Q, R, X, Y, and Z areeach preferably a substituted or unsubstituted alkyl sulfonyl grouphaving 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. As the examples of thesubstituent, mention may be made of the same ones as the substituents asmentioned when the G is a group capable of further having a substituent.Examples of the alkyl and aryl sulfonyl groups may include, for example,methyl sulfonyl, ethyl sulfonyl, phenyl sulfonyl, and p-toluenesulfonyl.

The acyl groups represented by Q, R, X, Y, and Z are each preferably aformyl group, a substituted or unsubstituted alkyl carbonyl group having2 to 30, a substituted or unsubstituted aryl carbonyl group having 7 to30 carbon atoms, a substituted or unsubstituted heterocyclic carbonylgroup having 4 to 30 carbon atoms, bonded to a carbonyl group through acarbon atom. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the acyl groups mayinclude, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl,benzoyl, p-n-octyloxy phenyl carbonyl, 2-pyridyl carbonyl, and 2-furylcarbonyl.

The aryloxy carbonyl groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted aryloxy carbonyl group having7 to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of the aryloxycarbonyl group may include, for example, phenoxy carbonyl,o-chlorophenoxy carbonyl, m-nitrophenoxy carbonyl, and p-t-butyl phenoxycarbonyl.

The alkoxy carbonyl groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted alkoxy carbonyl group having 2to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of the alkoxycarbonyl group may include, for example, methoxy carbonyl, ethoxycarbonyl, t-butoxy carbonyl, and n-octadecyloxy carbonyl.

The carbamoyl groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted carbamoyl group having 1 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the carbamoyl groupmay include, for example, carbamoyl, N-methyl carbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octyl carbamoyl, and N-(methyl sulfonyl)carbamoyl.

The phosphino groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted phosphino group having 2 to 30carbon atoms. As the examples of the substituent, mention may be made ofthe same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the phosphinogroups may include, for example, dimethyl phosphino, diphenyl phosphino,and methyl phenoxy phosphino.

The phosphinyl groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted phosphinyl group having 2 to30 carbon atoms. As the examples of the substituent, mention may be madeof the same ones as the substituents as mentioned when the G is a groupcapable of further having a substituent. Examples of the phosphinylgroups may include, for example, phosphinyl, dioctyloxy phosphinyl, anddiethoxy phosphinyl.

The phosphinyloxy groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted phosphinyloxy group having 2to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of thephosphinyloxy groups may include, for example, diphenoxy phosphinyloxy,and dioctyloxy phosphinyloxy.

The phosphinyl amino groups represented by Q, R, X, Y, and Z are eachpreferably a substituted or unsubstituted phosphinyl amino group having2 to 30 carbon atoms. As the examples of the substituent, mention may bemade of the same ones as the substituents as mentioned when the G is agroup capable of further having a substituent. Examples of thephosphinyl amino group may include, for example, dimethoxy phosphinylamino, and dimethylamino phosphinyl amino.

The silyl groups represented by Q, R, X, Y, and Z are each preferably asubstituted or unsubstituted silyl group having 3 to 30 carbon atoms. Asthe examples of the substituent, mention may be made of the same ones asthe substituents as mentioned when the G is a group capable of furtherhaving a substituent. Examples of the silyl groups may include, forexample, trimethyl silyl, t-butyldimethyl silyl, and phenyldimethylsilyl.

Examples of the azo groups represented by Q, R, X, Y, and Z may includephenyl azo, 4-methoxyphenyl azo, 4-pivaloylamino phenyl azo, and2-hydroxy-4-propanoyl phenyl azo.

Examples of the imido group represented by Q, R, X, Y, and Z may includeN-succinimido and N-phthalimido.

When Q, R, X, Y, and Z each represent a divalent group, the divalentgroup is preferably an alkylene group (e.g., methylene, ethylene,propylene, butylene, pentylene), an alkenylene group (e.g., ethenyleneor propenylene), an alkynylene group (e.g., ethynylene or propynylene),an arylene group (e.g., phenylene or naphthalene), a divalentheterocyclic group (e.g., a 6-chloro-1,3,5-triazin-2,4-diyl group, apyrimidine 2,4-diyl group, a quinoxaline-2,3-diyl group, orpyridazine-3,6-diyl), —O—, —CO—, —NR′— (where R′ is a hydrogen atom, analkyl group, or an aryl group), —S—, —SO₂—, —SO—, or a combinationthereof (e.g., —NHCH₂CH₂NH—, or —NHCONH—).

An alkylene group, an alkenylene group, an alkynylene group, an arylenegroup, a divalent heterocyclic group, or an alkyl group or an aryl groupof R may have a substituent.

Examples of the substituent are the same as the substituents describedfor the G.

The alkyl group and the aryl group of the R′ are the same as theexamples of the substituent of the G.

Further preferably, they are each further preferably an alkylene grouphaving 10 or less carbon atoms, an alkenylene group having 10 or lesscarbon atoms, an alkynylene group having 10 or less carbon atoms, anarylene group having 6 or more and 10 or less carbon atoms, a divalentheterocyclic group, —S—, —SO—, —SO₂—, or a combination thereof (e.g.,—SCH₂CH₂S— or —SCH₂CH₂CH₂S—).

The total number of carbon atoms of the divalent linking group ispreferably 0 to 50, more preferably 0 to 30, and most preferably 0 to10.

When Q, R, X, Y, and Z each represent a trivalent group, the trivalentgroup is preferably an alkylene group, an alkenylene group, analkynylene group, an arylene group, a trivalent heterocyclic group, >N—,or a combination thereof (e.g., >NCH₂CH₂NH— or >NCONH—).

The total number of carbon atoms of the trivalent linking group ispreferably 0 to 50, more preferably 0 to 30, and most preferably 0 to10.

In the formula (I), preferred examples of n is 1 or 2, and in particularpreferably 2.

In the formula (I), preferred examples of a substituent of X is anelectron attracting group. It is particularly an electron attractinggroup with a Hammett's substituent constant σp value of 0.20 or more,and more preferably, it is preferably an electron attracting group witha σp value of 0.30 or more. It is an electron attracting group of 1.0 orless as the upper limit.

Specific examples of X which is an electron attracting group with a σpvalue of 0.20 or more may include an acyl group, an acyloxy group, acarbamoyl group, an alkyloxy carbonyl group, an aryloxy carbonyl group,a cyano group, a nitro group, a dialkyl phosphono group, a diarylphosphono group, a diaryl phosphinyl group, an alkyl sulfinyl group, anaryl sulfinyl group, an alkyl sulfonyl group, an aryl sulfonyl group, asulfonyloxy group, an acyl thio group, a sulfamoyl group, a thiocyanategroup, a thiocarbonyl group, an alkyl halide group, an alkoxy halidegroup, an aryloxy halide group, an alkylamino halide group, an alkylthio halide group, an aryl group substituted with another electronattracting group with a σp value of 0.20 or more, a heterocyclic group,a halogen atom, an azo group, or a selenocyanate group.

As preferred ones of X, mention may be made of an acyl group having 2 to12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, acarbamoyl group having 1 to 12 carbon atoms, an alkyloxy carbonyl grouphaving 2 to 12 carbon atoms, an aryloxy carbonyl group having 7 to 18carbon atoms, a cyano group, a nitro group, an alkyl sulfinyl grouphaving 1 to 12 carbon atoms, an aryl sulfinyl group having 6 to 18carbon atoms, an alkyl sulfonyl group having 1 to 12 carbon atoms, anaryl sulfonyl group having 6 to 18 carbon atoms, a sulfamoyl grouphaving 0 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbonatoms, an alkyloxy halide group having 1 to 12 carbon atoms, an alkylthio halide group having 1 to 12 carbon atoms, an aryloxy halide grouphaving 7 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms,substituted with two or more electron attracting groups with a σp of0.20 or more, and a heterocyclic group which has 1 to 18 carbon atoms,is 5- to 8-membered, and has a nitrogen atom, an oxygen atom, or asulfur atom.

Further preferably, mention may be made of a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an aryl sulfonyl grouphaving 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbonatoms.

As X, the particularly preferred ones are each a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having0 to 12 carbon atoms. Most preferred is a cyano group, or an alkylsulfonyl group having 1 to 12 carbon atoms.

In the formula (I), preferred examples of the substituent of Z show ahydrogen atom, a substituted or unsubstituted alkyl group, a substitutedor unsubstituted cycloalkyl group, a substituted or unsubstitutedalkenyl group, a substituted or unsubstituted alkynyl group, asubstituted or unsubstituted aralkyl group, a substituted orunsubstituted aryl group, or a substituted or unsubstituted heterocyclicgroup.

The detailed examples of the substituent represented by Z are the sameas the corresponding substituent examples described for the examples ofthe heterocyclic group represented by the G, and preferred examplesthereof are also the same.

The particularly preferred substituent represented by Z is preferably asubstituted aryl group, or a substituted heterocyclic group. Out ofthese, particularly, a substituted aryl group is preferred.

In the formula (I), preferred examples of the substituent of Q arepreferably a hydrogen atom, a substituted or unsubstituted alkyl group,a substituted or unsubstituted acyl group, a substituted orunsubstituted alkyl sulfonyl group, or a substituted or unsubstitutedaryl sulfonyl group. Particularly preferred is a hydrogen atom, asubstituted or unsubstituted alkyl group, or a substituted orunsubstituted acyl group. Out of these, particularly, a hydrogen atom ispreferred.

In the formula (I), R is preferably a substituted or unsubstituted totalcarbon number C1 to C12 alkyl group, a substituted or unsubstitutedtotal carbon number C6 to C18 aryl group, or a substituted orunsubstituted total carbon number C4 to C12 heterocyclic group. Out ofthese, a total carbon atom number C1 to C8 straight-chain alkyl group,or branched alkyl group is preferred. Particularly, a secondary ortertiary alkyl group is preferred, and a t-butyl group is mostpreferred.

In the formula (I), Y is preferably a hydrogen atom, a substituted orunsubstituted total carbon number C1 to C12 alkyl group, a substitutedor unsubstituted total carbon number C6 to C18 aryl group, or asubstituted or unsubstituted total carbon number C4 to C12 heterocyclicgroup. Out of these, a hydrogen atom, a total carbon atom number C1 toC8 straight-chain alkyl group, and or branched alkyl group is preferred.Particularly, a hydrogen atom, or a C1 to C8 alkyl group is preferred,and a hydrogen atom is most preferred.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (I) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (I) of the invention include the following(i) to (vii):

-   (i) G is preferably a 5- to 8-membered nitrogen-containing    heterocyclic ring. Particularly, a S-triazine ring, a pyramidine    ring, a pyridazine ring, a pyrazine ring, a pyridine ring, an    imidazole ring, a pyrazole ring, or a pyrrole ring is preferred. Out    of these, a S-triazine ring, a pyramidine ring, a pyridazine ring,    or a pyrazine ring is preferred. A S-triazine ring is most    preferred.-   (ii) R is preferably a substituted or unsubstituted total carbon    number C1 to C12 alkyl group, a substituted or unsubstituted total    carbon number C6 to C18 aryl group, or a substituted or    unsubstituted total carbon number C4 to C12 heterocyclic group. Out    of these, preferred is a total carbon atom number C1 to C8    straight-chain alkyl group or branched alkyl group. Particularly, a    secondary or tertiary alkyl group is preferred, and a t-butyl group    is most preferred.-   (iii) X is in particular preferably a cyano group, an alkyl sulfonyl    group having 1 to 12 carbon atoms, an aryl sulfonyl group having 6    to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon    atoms. Out of these, a cyano group, or an alkyl sulfonyl group    having 1 to 12 carbon atoms is preferred. Most preferred is a cyano    group.-   (iv) Y is preferably a hydrogen atom, a substituted or unsubstituted    total carbon number C1 to C12 alkyl group, a substituted or    unsubstituted total carbon number C6 to C18 aryl group, or a    substituted or unsubstituted total carbon number C4 to C12    heterocyclic group. Out of these, a hydrogen atom, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a hydrogen atom or a C1 to C8    alkyl group is preferred. A hydrogen atom is most preferred.-   (v) Z is preferably a hydrogen atom, a substituted or unsubstituted    alkyl group, a substituted or unsubstituted cycloalkyl group, a    substituted or unsubstituted alkenyl group, a substituted or    unsubstituted alkynyl group, a substituted or unsubstituted aralkyl    group, a substituted or unsubstituted aryl group, or a substituted    or unsubstituted heterocyclic group. The particularly preferred    substituent is a substituted aryl group or a substituted    heterocyclic group. Out of these, particularly, a substituted aryl    group is preferred.-   (vi) Q is preferably a hydrogen atom, a substituted or unsubstituted    alkyl group, a substituted or unsubstituted acyl group, a    substituted or unsubstituted alkyl sulfonyl group, or a substituted    or unsubstituted aryl sulfonyl group. Particularly, a hydrogen atom,    a substituted or unsubstituted alkyl group, or a substituted or    unsubstituted acyl group is preferred. Out of these, particularly, a    hydrogen atom is preferred.-   (vii) n represents an integer of 1 to 3, preferably 1 or 2, and    particularly most preferably 2.

Out of the azo coloring matters represented by the formula (I),preferred are the coloring matters represented by the following formulae(1) to (5):

Below, the formula (1) will be described in details.

R₁, R₂, X₁, X₂, Y₁, Y₂, Z₁, and Z₂ each represent a monovalent group.

The monovalent group represents a hydrogen atom, or a monovalentsubstituent. Examples of the monovalent substituent are the same as theexamples of the monovalent substituent of R,X,Y, and Z in the formula(I), and the preferred examples there of are also the same.

Below, the R₁, R₂, X₁, X₂, Y₁, Y₂, Z₁, and Z₂ will be further describedin details.

Examples of the substituents of R₁ and R₂ are each independently thesame as the examples of R in the formula (I), and the preferred examplesthereof are also the same.

Examples of the substituents of Y₁ and Y₂ are each independently thesame as the examples of Y in the formula (I), and the preferred examplesthereof are also the same.

Examples of the substituents of Z₁ and Z₂ are each independently thesame as the examples of Z in the formula (I), and the preferred examplesthereof are also the same.

Below, the G will be further described in details.

G represents an atomic group forming a 5- to 8-memberednitrogen-containing heterocyclic ring.

Preferred examples of the 5- to 8-membered nitrogen-containingheterocyclic ring represented by G may include a S-triazine ring, apyramidine ring, a pyridazine ring, a pyrazine ring, a pyridine ring, animidazole ring, a pyrazole ring, or a pyrrole ring. Out of these, aS-triazine ring, a pyramidine ring, a pyridazine ring, or a pyrazinering is more preferred. A S-triazine ring is most preferred.

Below, the M will be further described in details.

M represents a hydrogen atom or a cation.

The cation represented by M is an alkali metal ion, ammonium, or aquaternary ammonium cation, and preferably Li, Na, K, or NR₄. However,Rs are an alkyl group and an aryl group, and the same as the examples ofthe alkyl group and the aryl group represented by R and Y. Out of these,preferred examples of M include Li, Na, K, or NH₄, and Li, Na, or K isin particular preferred.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (1) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (1) of the invention include the following(i) to (vi):

-   (i) R₁ and R₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Out of these, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a secondary or tertiary alkyl    group is preferred, and a t-butyl group is most preferred.-   (ii) X₁ and X₂ may be the same or different. An electron attracting    group with a Hammett's substituent constant σp value of 0.20 or more    is preferred. Further, an electron attracting group with a σp value    of 0.30 or more is preferred. An electron attracting group of 1.0 or    less is preferred as the upper limit. Out of these, preferred is a    cyano group, an alkyl sulfonyl group having 1 to 12 carbon atoms, an    aryl sulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl    group having 0 to 12 carbon atoms. Most preferred is a cyano group    or an alkyl sulfonyl group having 1 to 12 carbon atoms.-   (iii) Y₁ and Y₂ may be the same or different. A hydrogen atom, a    substituted or unsubstituted total carbon number C1 to C12 alkyl    group, a substituted or unsubstituted total carbon number C6 to C18    aryl group, or a substituted or unsubstituted total carbon number C4    to C12 heterocyclic group is preferred. Further, a hydrogen atom, or    a substituted or unsubstituted alkyl group is preferred. Out of    these, a hydrogen atom is most preferred.-   (iv) Z₁ and Z₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to 12C alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Further, a substituted or    unsubstituted aryl group, or a substituted or unsubstituted    heterocyclic group is preferred. Particularly, a substituted aryl    group is most preferred.-   (v) G represents an atomic group forming a 5- to 8-membered    nitrogen-containing heterocyclic ring. Preferred examples of the 5-    to 8-membered nitrogen-containing heterocyclic ring include a    S-triazine ring, a pyramidine ring, a pyridazine ring, a pyrazine    ring, a pyridine ring, an imidazole ring, a pyrazole ring, or a    pyrrole ring. Out of these, a S-triazine ring, a pyramidine ring, a    pyridazine ring, or a pyrazine ring is more preferred. A S-triazine    ring is most preferred.-   (vi) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.

Below, the formula (2) will be described in details.

R₁, R₂, R₁₁, R₁₂, X₁, X₂, Z₁, and Z₂ each represent a monovalent group.

The monovalent group represents a hydrogen atom or a monovalentsubstituent.

L₁ represents a divalent linking group.

G₁ and G₂ each independently represent an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring.

M represents a hydrogen atom or a cation.

Below, the formula (2) will be further described in details.

In the formula (2), preferred examples of the substituents of R₁ and R₂are the same as the examples of the substituents of R₁, R₂, Y₁, and Y₂described for the formula (1), and the preferred examples thereof arealso the same.

In the formula (2), preferred examples of the substituents of X₁ and X₂are the same as the examples of the substituents of X₁ and X₂ describedfor the formula (1), and the preferred examples thereof are also thesame.

In the formula (2), preferred examples of the substituents of Z₁ and Z₂are the same as the examples of the substituents of Z₁ and Z₂ describedfor the formula (1), and the preferred examples thereof are also thesame.

In the formula (2), preferred examples of the substituents of G₁ and G₂are the same as the examples of the substituents of G described for theformula (1), and the preferred examples thereof are also the same.

In the formula (2), preferred examples of M are the same as the examplesof M described for the formula (1), and the preferred examples thereofare also the same.

In the formula (2), preferred examples of the substituents of R₁₁ andR₁₂ are the same as the examples of the substituents of R₁, R₂, Y₁, andY₂ described for the formula (1). Preferred examples thereof may includea —OM group (where M is a hydrogen atom or a cation), a substituted orunsubstituted amino group; an alkylamino group having 1 to 12 carbonatoms, an arylamino group having 6 to 18 carbon atoms, a substituted orunsubstituted alkyl thio group having 1 to 12 carbon atoms, and asubstituted or unsubstituted aryl thio group having 6 to 18 carbonatoms.

In the formula (2), the divalent linking group represented by L₁ ispreferably an alkylene group (e.g., methylene, ethylene, propylene,butylene, or pentylene), an alkenylene group (e.g., ethenylene orpropenylene), an alkynylene group (e.g., ethynylene or propynylene), anarylene group (e.g., phenylene or naphthylene), a divalent heterocyclicgroup (e.g., a 6-chloro-1,3,5-triazine-2,4-diyl group, a pyrimidine2,4-diyl group, a quinoxaline-2,3-diyl group, or a pyridazine-3,6-diyl),—O—, —CO—, —NR— (where R is a hydrogen atom, an alkyl group, or an arylgroup), —S—, —SO₂—, —SO—, or a combination thereof (e.g., —NHCH₂CH₂NH—or —NHCONH—).

An alkylene group, an alkenylene group, an alkynylene group, an arylenegroup, a divalent heterocyclic group, an alkyl group or an aryl group ofR may each have a substituent.

Examples of the substituent are the same as the substituents of R₁, R₂,Y₁, and Y₂ in the formula (1).

The alkyl groups and the aryl groups of the R are the same as theexamples of the substituents of R₁, R₂, Y₁, and Y₂ in the formula (1).

Further preferably, they are each further preferably an alkylene grouphaving 10 or less carbon atoms, an alkenylene group having 10 or lesscarbon atoms, an alkynylene group having 10 or less carbon atoms, anarylene group having 6 or more and 10 or less carbon atoms, —S—, —SO—,—SO₂—, or a combination thereof (e.g., —SCH₂CH₂S—, or —SCH₂CH₂CH₂S).

The total number of carbon atoms of the divalent linking group ispreferably 0 to 50, more preferably 0 to 30, and most preferably 0 to10.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (2) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (2) of the invention include the following(i) to (vii):

-   (i) R₁ and R₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Out of these, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a secondary or tertiary alkyl    group is preferred, and a t-butyl group is most preferred.-   (ii) X₁ and X₂ may be the same or different. An electron attracting    group with a Hammett's substituent constant σp value of 0.20 or more    is preferred. Further, an electron attracting group of 0.30 or more    is preferred. An electron attracting group of 1.0 or less is    preferred as the upper limit. Out of these, preferred is a cyano    group, an alkyl sulfonyl group having 1 to 12 carbon atoms, an aryl    sulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group    having 0 to 12 carbon atoms. Most preferred is a cyano group or an    alkyl sulfonyl group having 1 to 12 carbon atoms.-   (iii) Z₁ and Z₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Further, a substituted or    unsubstituted aryl group, or a substituted or unsubstituted    heterocyclic group is preferred. Particularly, a substituted aryl    group is most preferred.-   (iv) G₁ and G₂ may be the same or different, and each represent an    atomic group forming a 5- to 8-membered nitrogen-containing    heterocyclic ring. Preferred examples of the 5- to 8-membered    nitrogen-containing heterocyclic ring include a S-triazine ring, a    pyramidine ring, a pyridazine ring, a pyrazine ring, a pyridine    ring, an imidazole ring, a pyrazole ring, or a pyrrole ring. Out of    these, a S-triazine ring, a pyramidine ring, a pyridazine ring, or a    pyrazine ring is more preferred. A S-triazine ring is most    preferred.-   (v) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.-   (vi) R₁₁ and R₁₂ may be the same or different. They are each    preferably a —OM group (where M is a hydrogen atom or a cation), a    substituted or unsubstituted amino group (an alkylamino group having    1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon    atoms), a substituted or unsubstituted alkyl thio group having 1 to    12 carbon atoms, or a substituted or unsubstituted aryl thio group    having 6 to 18 carbon atoms. Out of these, an unsubstituted amino    group, an alkylamino group having 1 to 12 carbon atoms, an arylamino    group having 6 to 18 carbon atoms, a substituted or unsubstituted    alkyl thio group having 1 to 12 carbon atoms, or a substituted or    unsubstituted aryl thio group having 6 to 18 carbon atoms is    preferred. Particularly, an unsubstituted amino group, a    dialkylamino group having 1 to 12 carbon atoms, an arylamino group    having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl    thio group having 1 to 12 carbon atoms is preferred.-   (vii) L₁ is preferably an alkylene group having 10 or less carbon    atoms, an alkenylene group having 10 or less carbon atoms, an    alkynylene group having 10 or less carbon atoms, an arylene group    having 6 or more and 10 or less carbon atoms, —S—, —SO—, —SO₂—, or a    combination thereof (e.g., —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—). It is    further preferably an alkylene group having 10 or less carbon atoms,    an arylene group having 6 or more and 10 or less carbon atoms, —S—,    —SO—, —SO₂—, or a combination thereof (e.g., —SCH₂CH₂S—, or    —SCH₂CH₂CH₂S—). It is in particular preferably an alkylene group    having 10 or less carbon atoms, —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—.

Below, the formula (3) will be described in details.

R₁, R₂, R₁₁, R₁₂, X₁, X₂, Y₁, and Y₂ each represent a monovalent group.

The monovalent group represents a hydrogen atom or a monovalentsubstituent.

L₂ represents a divalent linking group.

G₁ and G₂ each independently represent an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring.

M represents a hydrogen atom or a cation.

Below, the formula (3) will be further described in details.

In the formula (3), preferred examples of the substituents of R₁, R₂,Y₁, and Y₂ are the same as the examples of the substituents of R₁, R₂,Y₁, and Y₂ described for the formula (1), and the preferred examplesthereof are also the same.

In the formula (3), preferred examples of the substituents of X₁ and X₂are the same as the examples of the substituents of X₁ and X₂ describedfor the formula (1), and the preferred examples thereof are also thesame.

In the formula (3), preferred examples of the substituents of G₁ and G₂are the same as the examples of the substituents of G described for theformula (1), and the preferred examples thereof are also the same.

In the formula (3), preferred examples of the substituents of M are thesame as the examples of the substituents of M described for the formula(1), and the preferred examples thereof are also the same.

In the formula (3), preferred examples of the substituents of R₁₁ andR₁₂ are the same as the examples of the substituents of R₁ and R₂described for the formula (2), and the preferred examples thereof arealso the same.

In the formula (3), the divalent linking groups represented by L₂ arethe same as the examples L₁ described for the formula (2), and thepreferred examples thereof are also the same.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (3) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (3) of the invention include the following(i) to (vii):

-   (i) R₁ and R₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Out of these, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a secondary or tertiary alkyl    group is preferred, and a t-butyl group is most preferred.-   (ii) X₁ and X₂ may be the same or different. An electron attracting    group with a Hammett's substituent constant σp value of 0.20 or more    is preferred. Further, an electron attracting group 0.30 or more is    preferred. An electron attracting group of 1.0 or less is preferred    as the upper limit. Out of these, preferred is a cyano group, an    alkyl sulfonyl group having 1 to 12 carbon atoms, an aryl sulfonyl    group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to    12 carbon atoms. Most preferred is a cyano group or an alkyl    sulfonyl group having 1 to 12 carbon atoms.-   (iii) Y₁ and Y₂ may be the same or different. A hydrogen atom, a    substituted or unsubstituted total carbon number C1 to C12 alkyl    group, a substituted or unsubstituted total carbon number C6 to C18    aryl group, or a substituted or unsubstituted total carbon number C4    to C12 heterocyclic group is preferred. Further, a hydrogen atom, or    a substituted or unsubstituted alkyl group is preferred. Out of    these, a hydrogen atom is most preferred.-   (iv) G₁ and G₂ may be the same or different, and each represent an    atomic group forming a 5- to 8-membered nitrogen-containing    heterocyclic ring. Preferred examples of the 5- to 8-membered    nitrogen-containing heterocyclic ring include a S-triazine ring, a    pyramidine ring, a pyridazine ring, a pyrazine ring, a pyridine    ring, an imidazole ring, a pyrazole ring, or a pyrrole ring. Out of    these, a S-triazine ring, a pyramidine ring, a pyridazine ring, or a    pyrazine ring is more preferred. A S-triazine ring is most    preferred.-   (v) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.-   (vi) R₁₁ and R₁₂ may be the same or different. They are each    preferably a —OM group (where M is a hydrogen atom or a cation), a    substituted or unsubstituted amino group (such as an alkylamino    group having 1 to 12 carbon atoms, or an arylamino group having 6 to    18 carbon atoms), a substituted or unsubstituted alkyl thio group    having 1 to 12 carbon atoms, and a substituted or unsubstituted aryl    thio group having 6 to 18 carbon atoms. Out of these, an    unsubstituted amino group, an alkylamino group having 1 to 12 carbon    atoms, an arylamino group having 6 to 18 carbon atoms, a substituted    or unsubstituted alkyl thio group having 1 to 12 carbon atoms, or a    substituted or unsubstituted aryl thio group having 6 to 18 carbon    atoms is preferred. Particularly, an unsubstituted amino group, a    dialkylamino group having 1 to 12 carbon atoms, an arylamino group    having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl    thio group having 1 to 12 is preferred.-   (vii) L₂ is preferably an alkylene group having 10 or less carbon    atoms, an alkenylene group having 10 or less carbon atoms, an    alkynylene group having 10 or less carbon atoms, an arylene group    having 6 or more and 10 or less carbon atoms, —S—, —SO—, —SO₂—, or a    combination thereof (e.g., —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—). It is    further preferably an alkylene group having 10 or less carbon atoms,    an arylene group having 6 or more and 10 or less carbon atoms, —S—,    —SO—, —SO₂—, or a combination thereof (e.g., —SCH₂CH₂S—, or    —SCH₂CH₂CH₂S—). It is in particular preferably an alkylene group    having 10 or less carbon atoms, —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—.

Below, the formula (4) will be described in details.

R₁₁, R₁₂, X₁, X₂, Y₁, Y₂, Z₁, and Z₂ each represent a monovalent group.

The monovalent group represents a hydrogen atom or a monovalentsubstituent.

L₃ represents a divalent linking group.

G₁ and G₂ each independently represent an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring.

M represents a hydrogen atom or a cation.

Below, the formula (4) will be further described in details.

In the formula (4), preferred examples of the substituents of Y₁, and Y₂are the same as the examples of the substituents of R₁, R₂, Y₁, and Y₂described for the formula (1), and the preferred examples thereof arealso the same.

In the formula (4), preferred examples of the substituents of X₁ and X₂are the same as the examples of the substituents of X₁ and X₂ describedfor the formula (1), and the preferred examples thereof are also thesame.

In the formula (4), preferred examples of the substituents of G₁ and G₂are the same as the examples of the substituents of G described for theformula (1), and the preferred examples thereof are also the same.

In the formula (4), preferred examples of M are the same as the examplesof M described for the formula (1), and the preferred examples thereofare also the same.

In the formula (4), preferred examples of the substituents of R₁₁ andR₁₂ are the same as the examples of the substituents of R₁₁ and R₁₂described for the formula (2), and the preferred examples thereof arealso the same.

In the formula (4), the divalent linking groups represented by L₃ arethe same as the examples of the substituents of L₁ described for theformula (2), and the preferred examples thereof are also the same.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (4) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (4) of the invention include the following(i) to (vii):

-   (i) Y₁ and Y₂ may be the same or different. A hydrogen atom, a    substituted or unsubstituted total carbon number C1 to C12 alkyl    group, a substituted or unsubstituted total carbon number C6 to C18    aryl group, or a substituted or unsubstituted total carbon number C4    to C12 heterocyclic group is preferred. Further, a hydrogen atom, or    a substituted or unsubstituted alkyl group is preferred. Out of    these, a hydrogen atom is most preferred.-   (ii) X₁ and X₂ may be the same or different. An electron attracting    group with a Hammett's substituent constant σp value of 0.20 or more    is preferred. Further, an electron attracting group of 0.30 or more    is preferred. An electron attracting group of 1.0 or less is    preferred as the upper limit. Out of these, preferred is a cyano    group, an alkyl sulfonyl group having 1 to 12 carbon atoms, an aryl    sulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group    having 0 to 12 carbon atoms. Most preferred is a cyano group or an    alkyl sulfonyl group having 1 to 12 carbon atoms.-   (iii) Z₁ and Z₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to 12C alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Further, a substituted or    unsubstituted aryl group, or a substituted or unsubstituted    heterocyclic group is preferred. Particularly, a substituted aryl    group is most preferred.-   (iv) G₁ and G₂ may be the same or different, and each represent an    atomic group forming a 5- to 8-membered nitrogen-containing    heterocyclic ring. Preferred examples of the 5- to 8-membered    nitrogen-containing heterocyclic ring include a S-triazine ring, a    pyramidine ring, a pyridazine ring, a pyrazine ring, a pyridine    ring, an imidazole ring, a pyrazole ring, or a pyrrole ring. Out of    these, a S-triazine ring, a pyramidine ring, a pyridazine ring, or a    pyrazine ring is more preferred. A S-triazine ring is most    preferred.-   (v) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.-   (vi) R₁₁ and R₁₂ may be the same or different. They are each    preferably a —OM group (where M is a hydrogen atom or a cation), a    substituted or unsubstituted amino group (such as an alkylamino    group having 1 to 12 carbon atoms, or an arylamino group having 6 to    18 carbon atoms), a substituted or unsubstituted alkyl thio group    having 1 to 12 carbon atoms, and a substituted or unsubstituted aryl    thio group having 6 to 18 carbon atoms. Out of these, an    unsubstituted amino group, an alkylamino group having 1 to 12 carbon    atoms, an arylamino group having 6 to 18 carbon atoms, a substituted    or unsubstituted alkyl thio group having 1 to 12 carbon atoms, or a    substituted or unsubstituted aryl thio group having 6 to 18 carbon    atoms is preferred. Particularly, an unsubstituted amino group, a    dialkylamino group having 1 to 12 carbon atoms, an arylamino group    having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl    thio group having 1 to 12 is preferred.-   (vii) L₃ is preferably an alkylene group having 10 or less carbon    atoms, an alkenylene group having 10 or less carbon atoms, an    alkynylene group having 10 or less carbon atoms, an arylene group    having 6 or more and 10 or less carbon atoms, —S—, —SO—, —SO₂—, or a    combination thereof (e.g., —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—). It is    further preferably an alkylene group having 10 or less carbon atoms,    an arylene group having 6 or more and 10 or less carbon atoms, —S—,    —SO—, —SO₂—, or a combination thereof (e.g., —SCH₂CH₂S—, or    —SCH₂CH₂CH₂S—). It is in particular preferably an alkylene group    having 10 or less carbon atoms, —SCH₂CH₂S—, or —SCH₂CH₂CH₂S—.

Below, the formula (5) will be described in details.

R₁, R₂, R₁₁, R₁₂, Y₁, Y₂, Z₁, and Z₂ each represent a monovalent group.

The monovalent group represents a hydrogen atom or a monovalentsubstituent.

L₄ represents a divalent linking group.

G₁ and G₂ each independently represent an atomic group forming a 5- to8-membered nitrogen-containing heterocyclic ring.

M represents a hydrogen atom or a cation.

Below, the formula (5) will be further described in details.

In the formula (5), preferred examples of the substituents of R₁, R₂,Y₁, and Y₂ are the same as the examples of the substituents of R₁, R₂,Y₁, and Y₂ described for the formula (1), and the preferred examplesthereof are also the same.

In the formula (5), preferred examples of the substituents of Z₁ and Z₂are the same as the examples of the substituents of Z₁ and Z₂ describedfor the formula (1), and the preferred examples thereof are also thesame.

In the formula (5), preferred examples of G₁ and G₂ are the same as theexamples of the substituents of G described for the formula (1), and thepreferred examples thereof are also the same.

In the formula (5), preferred examples of M are the same as the examplesof M described for the formula (1), and the preferred examples thereofare also the same.

In the formula (5), preferred examples of the substituents of R₁₁ andR₁₂ are the same as the examples of the substituents of R₁₁ and R₁₂described for the formula (2), and the preferred examples thereof arealso the same.

In the formula (5), the divalent linking groups represented by L₄ arethe same as the examples of the substituents of L₁ described for theformula (2), and the preferred examples thereof are also the same.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (5) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (5) of the invention include the following(i) to (vii):

-   (i) R₁ and R₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Out of these, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a secondary or tertiary alkyl    group is preferred, and a t-butyl group is most preferred.-   (ii) Y₁ and Y₂ may be the same or different. A hydrogen atom, a    substituted or unsubstituted total carbon number C1 to C12 alkyl    group, a substituted or unsubstituted total carbon number C6 to C18    aryl group, or a substituted or unsubstituted total carbon number C4    to C12 heterocyclic group is preferred. Further, a hydrogen atom, or    a substituted or unsubstituted alkyl group is preferred. Out of    these, a hydrogen atom is most preferred.-   (iii) Z₁ and Z₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to 12C alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Further, a substituted or    unsubstituted aryl group, or a substituted or unsubstituted    heterocyclic group is preferred. Particularly, a substituted aryl    group is most preferred.-   (iv) G₁ and G₂ may be the same or different, and each represent an    atomic group forming a 5- to 8-membered nitrogen-containing    heterocyclic ring. Preferred examples of the 5- to 8-membered    nitrogen-containing heterocyclic ring include a S-triazine ring, a    pyramidine ring, a pyridazine ring, a pyrazine ring, a pyridine    ring, an imidazole ring, a pyrazole ring, or a pyrrole ring. Out of    these, a S-triazine ring, a pyramidine ring, a pyridazine ring, or a    pyrazine ring is more preferred. A S-triazine ring is most    preferred.-   (v) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.-   (vi) R₁₁ and R₁₂ may be the same or different. They are each    preferably a —OM group (where M is a hydrogen atom or a cation), a    substituted or unsubstituted amino group; an alkylamino group having    1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon    atoms, a substituted or unsubstituted alkyl thio group having 1 to    12 carbon atoms, and a substituted or unsubstituted aryl thio group    having 6 to 18 carbon atoms. Out of these, an unsubstituted amino    group, an alkylamino group having 1 to 12 carbon atoms, an arylamino    group having 6 to 18 carbon atoms, a substituted or unsubstituted    alkyl thio group having 1 to 12 carbon atoms, or a substituted or    unsubstituted aryl thio group having 6 to 18 carbon atoms is    preferred. Particularly, an unsubstituted amino group, a    dialkylamino group having 1 to 12 carbon atoms, an arylamino group    having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl    thio group having 1 to 12 is preferred.-   (vii) L₄ is preferably a divalent linking group, and it is    preferably an electron attracting group with a Hammett's substituent    constant σp value of 0.20 or more, and further preferably an    electron attracting group of 0.30 or more. An electron attracting    group of 1.0 or less is preferred as the upper limit. Out of these,    preferred is an alkyl sulfonyl group having 1 to 12 carbon atoms:    {—SO₂—(CH₂)_(n)—O₂S—; n=an integer of 1 to 10}, or an aryl sulfonyl    group having 6 to 18 carbon atoms: {—SO₂—Ar—OS—; where Ar is    preferably a substituted or unsubstituted aryl group, and most    preferably an alkyl sulfonyl group having 1 to 12 carbon atoms:    {—SO₂—(CH₂)_(n)—O₂S—; n=an integer of 1 to 5}.

Out of the azo coloring matters represented by the formula (I),preferred are the coloring matters represented by the following formula(6):

Below, the formula (6) will be described in details.

R₁, R₂, Y₁, and Y₂ each represent a monovalent group, X₁ and X₂ eachindependently represent an electron attracting group with a Hammett'ssubstituent constant σp value of 0.20 or more. Z₁ and Z₂ eachindependently represent a hydrogen atom, a substituted or unsubstitutedalkyl group, a substituted or unsubstituted alkenyl group, a substitutedor unsubstituted alkynyl group, a substituted or unsubstituted aralkylgroup, a substituted or unsubstituted aryl group, or a substituted orunsubstituted heterocyclic group. M represents a hydrogen atom or acation.

Below, R₁, R₂, X₁, X₂, Y₁, Y₂, Z₁, Z₂, and M will be described indetails.

Examples of the substituents of R₁, R₂, Y₁, and Y₂ are the same as theexamples of the substituents of R₁, R₂, Y₁, and Y₂ described in theformula (1), and the preferred examples thereof are also the same.

Examples of the substituents of X₁ and X₂ are the same as the examplesof the substituents of X₁ and X₂ described for the formula (1), and thepreferred examples thereof are also the same.

Examples of the substituents of Z₁ and Z₂ are the same as the examplesof the substituents of Z₁ and Z₂ described in the formula (1), and thepreferred examples thereof are also the same.

Examples of M are the same as the examples of M described in the formula(1), and the preferred examples thereof are also the same.

As for the combination of the preferred substituents of the coloringmatter represented by the formula (6) of the invention, preferred is acompound in which at least one of various substituents is the preferredgroup. More preferred is a compound in which a larger number of varioussubstituents are the preferred groups. Most preferred is a compound inwhich all the substituents are the preferred substituents.

The particularly preferred combinations for the coloring matterrepresented by the formula (6) of the invention include the following(i) to (vi):

-   (i) R₁ and R₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to C12 alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Out of these, a total carbon    atom number C1 to C8 straight-chain alkyl group or branched alkyl    group is preferred. Particularly, a secondary or tertiary alkyl    group is preferred, and a t-butyl group is most preferred.-   (ii) X₁ and X₂ may be the same or different. An electron attracting    group with a Hammett's substituent constant σp value of 0.20 or more    is preferred. Further, an electron attracting group of 0.30 or more    is preferred. An electron attracting group of 1.0 or less is    preferred as the upper limit. Out of these, preferred is a cyano    group, an alkyl sulfonyl group having 1 to 12 carbon atoms, an aryl    sulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group    having 0 to 12 carbon atoms. Most preferred is a cyano group or an    alkyl sulfonyl group having 1 to 12 carbon atoms.-   (iii) Y₁ and Y₂ may be the same or different. A hydrogen atom, a    substituted or unsubstituted total carbon number C1 to C12 alkyl    group, a substituted or unsubstituted total carbon number C6 to C18    aryl group, or a substituted or unsubstituted total carbon number C4    to C12 heterocyclic group is preferred. Further, a hydrogen atom, or    a substituted or unsubstituted alkyl group is preferred. Out of    these, a hydrogen atom is most preferred.-   (iv) Z₁ and Z₂ may be the same or different. A substituted or    unsubstituted total carbon number C1 to 12C alkyl group, a    substituted or unsubstituted total carbon number C6 to C18 aryl    group, or a substituted or unsubstituted total carbon number C4 to    C12 heterocyclic group is preferred. Further, a substituted or    unsubstituted aryl group, or a substituted or unsubstituted    heterocyclic group is preferred. Particularly, a substituted aryl    group is most preferred.-   (v) M is preferably a hydrogen atom or a cation, in particular    preferably a hydrogen atom, an alkali metal ion, ammonium, or a    quaternary ammonium cation, and further preferably Li, Na, K, or    NH₄.

In the invention, when the compounds represented by the formulae (I),(1), (2), (3), (4), (5), and (6) are required to have hydrophilicity,each compound preferably has two or more ionic hydrophilic groups in themolecule, further preferably has 2 to 10 ionic hydrophilic groups, andin particular preferably has 3 to 6 hydrophilic groups.

However, when water is not used as the medium, the compound is notrequired to have an ionic hydrophilic group.

As the ionic hydrophilic group, any group is acceptable so long as it isan ionic dissociation group. Specifically, mention may be made of asulfo group, a carboxyl group (including a salt thereof), a hydroxylgroup (which may be in the form of a salt), a phosphono group (which maybe in the form of a salt), or a quaternary ammonium.

Preferred is a sulfo group, a carboxyl group, or a hydroxyl group(including a salt thereof).

When the ionic hydrophilic group is a salt, preferred countercations arean alkali metal (e.g., lithium, sodium, or potassium), ammonium, and anorganic cation (e.g., pyridinium, tetramethyl ammonium, or guadinium).Out of these, an alkali metal is preferred. Particularly, for a sulfogroup, a lithium salt is preferred, and for a carboxy group, a sodiumsalt and or a potassium salt is preferred.

As for the water soluble coloring matter represented by the formulae(I), (1), (2), (3), (4), (5), and (6), from the viewpoint of colorreproduction, it preferably has a maximum absorption wavelength (λmax)of 380 to 490 nm in H₂O, further preferably has a λmax of 400 to 480 nm,and in particular preferably has a λmax of 420 to 460 nm.

Specific examples of the coloring matter represented by the formulae(I), (1), (2), (3), (4), (5), and (6) (exemplified coloring mattersDYE-1 to -26) will be shown below. However, the coloring matters for usein the invention are not limited to the following examples.

Whereas, the structure of the following specific examples is shown inthe form of a free acid. However, it is naturally understood that eachexample may be used in the form of a given salt.

As preferred countercation, mention may be made of an alkali metal(e.g., lithium, sodium, or potassium), ammonium, or an organic cation(e.g., pyridinium, tetramethyl ammonium, or guadinium).

Then, the compound represented by the formula (7) in the invention willbe described in details.

The compounds represented by the formula (7) include a compound, and asalt thereof and a hydrate thereof.

The compounds represented by the formula (7) are useful novel compoundsas organic photoconductive materials, light recording materials, orfunctional materials such as medicinals and agrochemicals other thandyes or pigments. Particularly, they are useful as syntheticintermediates for novel azo coloring matters/azomethine coloringmatters.

In the formula (7), R₃ and R₄ are each independently the same as R₁ andR₂ represented by the formula (2), and the preferred examples thereofare also the same.

In the formula (7), P₁ and P₂ each independently represent a hydrogenatom or a leaving group.

In this specification, the leaving group denotes a group which leavesupon a chemical reaction. For example, it is a group which leaves uponthe coupling reaction with diazonium salt, or a group which causes theaddition elimination reaction of the oxidized of a phenylene diaminederivative with ease. Preferred examples of P₁ and P₂ may include ahydrogen atom, a halogen atom, an alkyloxy group, an aryloxy group, analkyl thio group, or an aryl thio group. Out of these, a hydrogen atomor a halogen atom is preferred. Out of these, a hydrogen atom ispreferable.

The methods for synthesizing the coloring matter or the intermediate ofthe invention will be described in details.

<1> Synthesis of Coupling Component

The coupling component (coloring matter intermediate which reacts with adiazonium salt, and derives therefrom an azo dyestuff) for use insynthesis of the coloring matter of the invention is preferably thecompound represented by the following formula (8).

R, G, and Q in the formula (8) are each independently the same as R, G,and Q in the formula (I), and the preferred examples thereof are alsothe same.

In the formula (8), n represents an integer of 1 to 3.

P represents a hydrogen atom or a leaving group. The leaving groupdenotes a group which leaves upon a chemical reaction. For example, itrepresents a group which leaves upon the coupling reaction with adiazonium salt, and a group which effects the addition eliminationreaction with the oxidized product of a phenylene diamine derivativewith ease. Preferred examples of P may include a hydrogen atom, ahalogen atom, an alkyloxy group, aryloxy group, an alkyl thio group, oran aryl thio group. Out of these, a hydrogen atom or a halogen atom ispreferred, and a hydrogen atom is most preferred.

Further preferred examples of the coupling component represented by theformula (8) are the compounds represented by the following formula (9),and salts or hydrates thereof.

In the formula (9), the substituents R, G, and P are respectively thesame as R, G, and P in the formula (8), and preferred examples thereofare also the same. Incidentally, the compounds represented by theformula (7) are included in the compounds represented by the formula(9).

In the formula (9), M represents a hydrogen atom or a cation.

When M represents a cation, it is the same as M in the formula (1), andpreferred examples thereof are also the same.

Particularly preferred examples of the coupling component represented bythe formula (9) are the compounds represented by the following formula(10), or salts or hydrates thereof.

In the formula (10), substituents R's are each independently the same asR's in the formula (8), and preferred examples thereof are also thesame.

In the formula (10), M is the same as M in the formula (9), andpreferred examples thereof are also the same.

Below, a method for synthesizing the coupling component represented bythe formula (9) will be described.

The compound represented by the formula (9) can be obtained, forexample, according to the following process.

Through a step (a) of allowing a base to act on a mixture of an organiccompound (α) having a halogen atom eliminable with hydrazine and water,and a step (b) of mixing the reaction solution obtained in the step (a)and hydrazine, a hydrazine derivative is obtained. Then, from a step (c)of allowing the hydrazine derivative obtained in the step (b) to reactwith an acylacetonitrile compound in the presence of an acid and anorganic solvent, the compound represented by the formula (9); (which ishereinafter referred to as a 5-aminopyrazole compound) is synthesized.

Examples of the organic compound (a) are cyanuric chloride,2-chloropyrimidine, 3-chloropyridazine, 3,5-dichloropyridazine,5-chloropyrazole, or 2-chloroimidazole. Preferred is cyanuric chloride,3,5-dichloro pyridazine, or 2-chloroimidazole.

First, as the step (a), a base is allowed to act on a mixture of theorganic compound (α) and water. In the invention, water can be used inthis manner as a preferable reaction solvent for manufacturing ahydrazine derivative. The amount of water to be used based on the amountof the organic compound (α) is preferably 0.5 to 50 times by mass, andmore preferably 1 to 20 times by mass.

In the invention, the organic compound (α) is preferably in a statedispersed in water. However, it can be in the form of an aqueoussolution according to the type of the organic compound (α).

Whereas, the solvent for the mixture of the organic compound (α) andwater mainly contains water as described above (10 to 100 mass %, andpreferably 50 to 100 mass % based on the total amount of the solvent).However, if required, other solvents than water can be used. As suchsolvents, mention may be made of dimethylformamide, dimethylacetamide,dimethylsulfoxide, and the like.

The bases include inorganic bases and organic bases. As the inorganicbases, mention may be made of sodium hydroxide, lithium hydroxide,potassium hydroxide, sodium hydrogen carbonate, sodium carbonate,potassium carbonate, potassium acetate, sodium acetate, lithium acetate,and the like, preferred is sodium hydroxide, sodium hydrogen carbonate,or potassium carbonate. Further preferred is sodium hydrogen carbonate,or sodium hydroxide. As the organic bases, mention may be made ofammonia, hydrazine, triethylamine, diazo bicyclo undecene, pyridine,2,6-dimethyl pyridine, dimethylaminopyridine, and the like. Preferred isammonia, hydrazine, triethylamine, or pyridine. Further preferred isammonia, or hydrazine. The amount of the base to be used is preferably0.05 to 30.0 equivalents, and more preferably 0.5 to 15.0 equivalentsbased on the amount of the organic compound (α) to be used.

The reaction temperature is preferably 5° C. to 80° C., and morepreferably 10° C. to 60° C.

The reaction time is preferably 30 minutes to 6 hours, and morepreferably 1 hour to 3 hours.

Subsequently, as the step (b), the reaction solution obtained in thestep (a) and hydrazine are mixed, and allowed to react with other,thereby to produce a hydrazine derivative. The mixing ratio of theorganic compound (α) and hydrazine is, for example, preferably 1:1 to1:20, and more preferably 1:2 to 1:10 in terms of the former:the latter(molar ratio).

The reaction temperature in the step (b) is preferably 0° C. to 90° C.,more preferably 0° C. to 80° C., and further preferably 0° C. to 65° C.When it is less than 0° C., the reaction rate is remarkably slowed, andthe length of time required for the synthesis becomes remarkably long.Therefore, this is uneconomical. Whereas, when the synthesis is carriedout at a temperature as high as more than 90° C., the amount ofby-products formed increases. Therefore this is not preferable.

The reaction time in the step (b) is preferably from 30 minutes to 300minutes, more preferably from 30 minutes to 200 minutes, and furtherpreferably 30 minutes to 150 minutes.

The reaction scheme when as the organic compound (α), cyanuric chlorideis used, and as the base, sodium hydrogen carbonate is used will beshown below.

The hydrazine derivative can be allowed to react with anacylacetonitrile compound in the presence of an acid and an organicsolvent, thereby to synthesize a 5-aminopyrazole compound.

This hydrazine derivative may be either the one produced according tothis application, or the one produced according to other method thanthis application.

As the organic solvent, there is particularly demanded a solvent inwhich an intermediate including a hydrazine derivative and anacylacetonitrile compound added thereto (which is hereinafter simplyreferred to as an intermediate) is dissolved, and in which a5-aminopyrazole compound is precipitated from the reaction system tosuppress the formation of the reaction by-products.

In the invention, the organic solvent is a solvent which does not causea liquid separation phenomenon during the reaction, and provides auniform solution with the solvent. Examples thereof may includealcoholic organic solvents such as methanol, ethanol, propanol,isopropanol, butanol, t-butyl alcohol, and amyl alcohol, ketone typeorganic solvents such as acetone and methyl ethyl ketone, diol typeorganic solvents such as ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, and 1,3-propanediol, ethertype organic solvents such as ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, and ethylene glycol diethyl ether,tetrahydrofuran, dioxane, and acetonitrile. These solvents may be usedas a mixed solution of two or more thereof.

Preferred are the organic solvents with a polarity parameter (ET) valueof 40 or more. Out of these, preferred are glycol type solvents havingtwo or more hydroxyl groups in the solvent molecule, or alcoholicsolvents having 3 or less carbon atoms, and preferably an alcoholsolvents having 2 or less carbon atoms. Further, mixed solvents thereofare also included.

As organic solvents, especially, an organic solvent having a hydroxylgroup is preferred. More preferred examples of alcohol may includemethanol and ethanol. Further, glycols such as oligo- (particularly, di-and tri-), and poly-C₂ to C₄-alkylene glycols are also preferred.Whereas, ethylene-based compounds are also advantageous. Examplesthereof may include ethylene glycol, 1,2-, and 1,3-propylene glycol,diethylene glycol, butylene glycol, di-, tri-, and tetra-ethyleneglycol, di-, tri-, and tetra-propylene glycol, polyethylene- andpolypropylene glycol, and glycerin.

More preferred examples may include methanol, ethylene glycol,diethylene glycol, triethylene glycol, polypropylene glycol, propyleneglycol, dipropylene glycol, glycerin, a 1:2 (v/v) mixed solvent ofethylene glycol and diethylene glycol, a 3:1 (v/v) of propylene glycoland triethylene glycol, a 1:2 to 3 (v/v) of methanol and ethyleneglycol, and a 1:2 to 5 (v/v) mixed solvent of methanol and triethyleneglycol. The amount of the solvent to be used is 1 to 100 times by mass,preferably 1 to 50 times by mass, and further preferably 1 to 20 timesby mass based on the amount of the compound represented by the formula(1).

The acid has no particular restriction. However, inorganic acids such ashydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid, andorganic acids such as methane sulfonic acid are also effective. Theamount of the acid used is 1 to 100 times by mass, preferably 1 to 20times by mass, and further preferably 1 to 10 times by mass based on theamount of the hydrazine derivative. When the amount of the acid issmall, the solubility of the intermediate is inferior, and the reactiontime becomes long. When the amount of the acid is too large, a largeamount of by-products are formed, which may incur degradation in yield.

As the acyl groups in the acylacetonitrile compound, mention may be madeof an acetyl group, a pivaloyl group, an isopropyl carbonyl group, aphenethyl carbonyl group, a 2-naphthyl carbonyl group, a 2-pyridylcarbonyl group, and the like. Particularly preferred is an acetyl group,a pivaloyl group, an isopropyl carbonyl group, or a phenethyl carbonylgroup.

The acylacetonitrile compound is added in a ratio of preferably 1 to 5mol, and more preferably 1 to 3 mol per mol of hydrazine of thehydrazine derivative.

The reaction temperature for the hydrazine derivative and theacylacetonitrile compound is preferably 0° C. to 120° C., morepreferably 0° C. to 100° C., and further preferably 0° C. to 75° C.

The reaction time is preferably 1 hour to 20 hours, more preferably 1hour to 15 hours, and further preferably 1 hour to 10 hours.

There will be shown below the reaction scheme of a series of steps of amethod for producing a hydrazine derivative of the invention, and amethod for producing a 5-aminopyrazole compound using the hydrazinederivative produced thereby. Incidentally, in the following scheme,there is shown the case where as the organic compound (α) of thestarting material, cyanuric chloride; as the base, sodium hydrogencarbonate; as the acylacetonitrile compound, pivaloyl acetonitrile; asthe acid, hydrochloric acid; and as the organic solvent, a mixed solventof methanol and ethylene glycol are used. However, the invention is notlimited thereto.

<2> Synthesis of Diazo Component:

The diazo component (coloring matter intermediate for deriving therefroma diazonium salt) for use in synthesizing the coloring matter of theinvention is preferably the compound represented by the followingformula (11).

The substituents X, Y, and Z in the formula (11) are the same as X, Y,and Z in the formula (I), respectively, and preferred examples thereofare also the same.

The compound represented by the formula (11) can be obtained, forexample, in accordance with the following reaction formula. In theformula, R represents a lower alkyl group, and —OW represents a leavinggroup.

<3> Synthesis of Azo Coloring Matter of the Invention:

The coloring matter of the invention can be synthesized in the followingmanner. For example, the diazonium salt obtained by preparing the diazocomponent of the formula (11) with a known method is allowed to undergoan azo coupling reaction with the coupling component of the formula (8)or (9).

The diazonium salt preparation and coupling reaction can be carried outby conventional methods.

To the preparation of the diazonium salt of the formula (11), forexample, there can be applied a conventional diazonium salt preparationmethod in which in an acid (e.g., hydrochloric acid, sulfuric acid,phosphoric acid, acetic acid, propionic acid, methane sulfonic acid, ortrifluoromethane sulfonic acid)-containing reaction medium, anitrosonium ion source such as nitrous acid, nitrite, or nitrosylsulfuric acid is used.

As more preferred examples of the acids, mention may be made of thecases where acetic acid, propionic acid, methane sulfonic acid,phosphoric acid, and sulfuric acid are used alone or in combination. Outof these, particularly preferred are the system of use in combination ofacetic acid and or propionic acid, and sulfuric acid.

As preferred examples of the reaction medium (solvent), use of organicacids or inorganic acids is preferable. Particularly, phosphoric acid,sulfuric acid, acetic acid, propionic acid, and methane sulfonic acidare preferred. Out of these, acetic acid and or propionic acid ispreferred.

As a preferred example of the nitrosonium ion source, use of nitrosylsulfuric acid in the preferred acid-containing reaction medium canprepare a diazonium salt with stability and with efficiency

The amount of the solvent to be used based on the diazo component of theformula (11) is preferably 0.5 to 50 times by mass, more preferably 1 to20 times by mass, and in particular preferably 3 to 10 times by mass.

In the invention, the diazo component of the formula (11) may be eitherin a state dispersed in water, or in the form of a dissolved solutionaccording to the type of the diazo component.

The amount of the nitrosonium ion source to be used is preferably 0.95to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, and inparticular preferably 1.00 to 1.10 equivalents based on the amount ofthe diazo component.

The reaction temperature is preferably −15° C. to 30° C., morepreferably −10° C. to 10° C., and further preferably −5° C. to 5° C.When it is less than −10° C., the reaction rate is remarkably slowed,and the length of time required for the synthesis becomes remarkablylong. Therefore, this is uneconomical. Whereas, when the synthesis iscarried out at a temperature as high as more than 30° C., the amount ofby-products formed increases. Therefore this is not preferable.

The reaction time is preferably from 30 minutes to 300 minutes, morepreferably from 30 minutes to 200 minutes, and further preferably 30minutes to 150 minutes.

The coupling reaction (azo coloring matter preparation step) can becarried out in an acidic reaction medium to in a basic reaction medium.However, for the azo coloring matter of the invention, the reaction ispreferably carried out in an acidic to neutral reaction medium.Particularly, carrying out of the reaction in an acidic reaction mediumcan suppress the decomposition of the diazonium salt, and can induce itto an azo coloring matter with efficiency.

As preferred examples of the reaction medium (solvent), organic acids,inorganic acids, or organic solvents can be used. However, particularly,organic solvents are preferred, and a solvent is preferred which doesnot cause a liquid separation phenomenon during the reaction, andprovides a uniform solution with the solvent. Examples thereof mayinclude alcoholic organic solvents such as methanol, ethanol, propanol,isopropanol, butanol, t-butyl alcohol, and amyl alcohol, ketone typeorganic solvents such as acetone and methyl ethyl ketone, diol typeorganic solvents such as ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, and 1,3-propanediol, ethertype organic solvents such as ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, and ethylene glycol diethyl ether,tetrahydrofuran, dioxane, and acetonitrile. These solvents may be usedas a mixed solution of two or more thereof.

Preferred are the organic solvents with a polarity parameter (ET) valueof 40 or more. Out of these, preferred are glycol type solvents havingtwo or more hydroxyl groups in the solvent molecule, or alcoholicsolvents having 3 or less carbon atoms, and preferably an alcoholsolvent having 2 or less carbon atoms (e.g., methanol, or ethanol).Further, mixed solvents thereof are also included.

The amount of the solvent to be used is preferably 1 to 100 times bymass, more preferably 1 to 50 times by mass, and further preferably 2 to10 times by mass based on the amount of the coupling componentrepresented by the formula (8) or (9).

In the invention, the coupling component represented by the formula (8)or (9) may be either in a state dispersed in a solvent, or in the formof a dissolved solution according to the type of the coupling component.

As for the amount of the coupling component to be used, the azocomponent is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to3.00 equivalents, and in particular preferably 1.00 to 1.50 equivalentsbased on the amount of the azo coupling moiety.

The reaction temperature is preferably −30° C. to 30° C., morepreferably −15° C. to 10° C., and further preferably −10° C. to 5° C.When it is less than −30° C., the reaction rate is remarkably slowed,and the length of time required for the synthesis becomes remarkablylong. Therefore, this is uneconomical. Whereas, when the synthesis iscarried out at a temperature as high as more than 30° C., the amount ofby-products formed increases. Therefore this is not preferable.

The reaction time is preferably from 30 minutes to 300 minutes, morepreferably from 30 minutes to 200 minutes, and further preferably 30minutes to 150 minutes.

In the method for synthesizing an azo coloring matter of the invention,the product (azo coloring matter) obtained by these reactions can bemade available with purification or without purification after havingbeen treated according to a common post-treatment method of an organicsynthesis reaction.

Namely, for example, the one freed from the reaction system can be madeavailable without purification, or by carrying out purificationoperations by recrystallization, salt formation, column chromatography(e.g., gel permeation chromatography (SEPHADEX™ LH-20: manufactured byPharmacia), and the like alone or in combination.

Alternatively, after the completion of the reaction, the reactionsolvent is distilled away, or is not distilled away, and the product ispoured into water or ice, followed by neutralization, or not followed byneutralization. The thus freed one can also be made available withoutpurification, or after carrying out purification operations byrecrystallization, salt formation, column chromatography, and the likealone or in combination.

Further alternatively, after the completion of the reaction, thereaction solvent is distilled away, or is not distilled away, and theproduct is poured into water or ice, followed by neutralization, or notfollowed by neutralization. The one extracted with an organicsolvent/aqueous solution can also be made available withoutpurification, or after carrying out purification operations byrecrystallization, salt formation, column chromatography, and the likealone or in combination.

As the uses of the coloring matter of the invention, mention may be madeof image recording materials for forming images, particularly, colorimages. Specifically, mention may be made of recording materials for inkjet system described below in details, and in addition, heat sensitiverecording materials, pressure sensitive recording materials, recordingmaterials using an electrophotographic system, transfer type silverhalide light sensitive materials, printing inks, recording pens, and thelike. Preferably, mention may be made of recording materials for ink jetsystem, heat sensitive transfer type recording materials, and recordingmaterials using an electrophotographic system. Further preferably,mention may be made of recording materials for ink jet system.

Whereas, the compounds are also applicable to color filters forrecording/reproducing color images for use in solid-state image pickupdevices such as CCDs, and displays such as LCDs and PDPs, and dyeingsolutions for dyeing various fibers.

The coloring matter of the invention are used by having been adjusted inphysical properties such as solubility, dispersibility, and thermaltransfer property suitable for the intended use by substituents.Further, the coloring matters of the invention are also usable indissolved state, in emulsion dispersed state, and further in soliddispersion state according to the system used.

[Ink]

The ink of the invention denotes an ink containing at least one coloringmatter of the invention.

The ink of the invention can contain medium. It is particularly suitableas ink for ink jet recording when a solvent is used as the medium. Theink of the invention can be manufactured by using an oleophilic mediumor an aqueous medium as the medium, and dissolving and/or dispersing thecoloring matter of the invention therein. Preferred is the case where anaqueous medium is used. The ink of the invention includes a compositionfor ink exclusive of the medium. If required, other additives may becontained in the ink of the invention in such a range not to impair theeffects of the invention. Examples of other additives may include knownadditives such as an anti-drying agent (wetting agent), an antifadingagent, an emulsion stabilizer, a penetration accelerator, a UV absorber,an antiseptic agent, an antifungal agent, a pH adjuster, a surfacetension regulator, an antifoaming agent, a viscosity modifier, adispersant, a dispersion stabilizer, a rust inhibitor, and a chelatingagent (described in JP-A-2003-306623). These various additives aredirectly added to an ink solution for a water soluble ink. When anoleophilic dye is used in the form of a dispersion, generally, it isadded to the dispersion after preparation of a dye dispersion. However,it may be added to an oil phase or a water phase for the preparation.

When the coloring matter of the invention is dispersed in an aqueousmedium, preferably, as in JP-A-11-286637, JP-A-2001-240763 (JapanesePatent Application No. 2000-78491), JP-A-2001-262039 (Japanese PatentApplication No. 2000-80259), and JP-A-2001-247788 (Japanese PatentApplication No. 2000-62370), colored fine particles containing acoloring matter and an oil soluble polymer are dispersed in an aqueousmedium, or as in JP-A-2001-262018 (Japanese Patent Application No.2000-78454), JP-A-2001-240763 (Japanese Patent Application No.2000-78491), and JP-A-2001-335734 (JP-A-2000-203856), the coloringmatter of the invention dissolved in a high boiling point organicsolvent is dispersed in an aqueous medium. As the specific method fordispersing the coloring matter of the invention in an aqueous medium,the oil soluble polymer, the high boiling point organic solvent, andadditives, to be used, and the amount of the materials used, thosedescribed in the foregoing patent publications may be preferably used.Alternatively, the azo coloring matter may also be dispersed in the formof fine particles still in solid form. For dispersion, a dispersant or asurfactant is usable.

As the dispersing devices, there can be used a simple stirrer orimpeller stirring system, an in-line stirring system, a mill system(such as a colloid mill, a ball mill, a sand mill, an attritor, a rollmill, or an agitator mill), an ultrasonic system, a high-pressureemulsifying and dispersing system (high-pressure homogenizer; asspecific commercially available devices, Gaulin Homogenizer,Microfluidizer, DeBEE2000, and the like). The details of the method forpreparing the ink jet recording ink are described in, other than theforegoing patent publications, respective publications of JP-A-5-148436,JP-A-5-295312, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584,JP-A-11-286637, JP-A-2001-2271003 (Japanese Patent Application No.2000-87539), which is also usable for the preparation of the ink jetrecording ink of the invention.

As the aqueous medium, a mixture containing water as a main component,and if desired, containing a water-miscible organic solvent addedtherein can be used. As the examples of the water-miscible organicsolvent, those described in JP-A-2003-306623 are usable. Incidentally,the water-miscible organic solvents may also be used in combination oftwo or more thereof.

The coloring matter of the invention is preferably contained in anamount of 0.1 part by mass or more and 20 parts by mass or less, morepreferably contained in an amount of 0.2 part by mass or more and 10parts by mass or less, and further preferably contained in an amount of0.5 to 9 parts by mass per 100 parts by mass of the ink jet recordingink of the invention. Further, the ink for ink jet of the invention,other coloring matters may be used in combination with the coloringmatter of the invention. When two or more coloring matters are used incombination, the total amount of the coloring matters containedpreferably falls within the foregoing range.

The ink of the invention may be used not only for the formation of amonochrome image but also for the formation of a full color image. Forthe formation of a full color image, a magenta tone ink, a cyan toneink, and a yellow tone ink can be used. Further, for adjusting the tone,a black tone ink may further be used.

Further, the ink for ink jet recording of the invention can use, otherthan the coloring matter in the invention, other yellow dyes at the sametime. As the applicable yellow dyes, the applicable magenta dyes, andthe applicable cyan dyes, given ones can be used, respectively. However,respective dyes described in paragraph Nos. 0090 to 0092 ofJP-A-2003-306623 are usable. As the applicable black materials, mentionmay be made of, other than disazo, trisazo, and tetraazo dyes, adispersion of carbon black.

[Ink Jet Recording Method]

The ink jet recording method of the invention provides energy to the inkjet recording ink, and forms images on known image receiving materials,i.e., ordinary paper and resin-coated paper, such as ink jet-specificpaper, film, electrophotographic common paper, cloth, glass, metal,ceramic, or the like described in JP-A-8-169172, JP-A-8-27693,JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62--238783,JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947,JP-A-10-217597, and JP-A-10-337947. Incidentally, as the ink jetrecording method of the invention, the description of paragraph Nos.0093 to 0105 of JP-A-2003-306623 is applicable.

For the formation of an image, a polymer latex compound may be used incombination for the purpose of imparting the glossiness or the waterresistance, or improving the weatherability. The timing of imparting thepolymer latex to the image receiving material may be before or afterimparting the colorant or simultaneously with it. Accordingly, thereceiving site may be in the image receiving paper or in the ink.Alternatively, the polymer latex may be used in the form of a liquidmaterial of the polymer latex alone. Specifically, the methods describedin JP-A-2002-166638 (Japanese Patent Application No. 2000-363090),JP-A-2002-121440 (Japanese Patent Application No. 2000-315231),JP-A-2002-154201 (Japanese Patent Application No. 2000-354380),JP-A-2002-144696 (Japanese Patent Application No. 2000-343944),JP-A-080759 (Japanese Patent Application No. 2000-268952), and JapanesePatent Application Nos. 2000-299465 and 2000-297365 may be preferablyused.

[Color Toner]

The content of the coloring matter of the invention per 100 parts bymass of the color toner of the invention has no particular restriction.However, it is preferably 0.1 part by mass or more, more preferably 1 to20 parts by mass, and most preferably 2 to 10 parts by mass.

As the color toner binder resins for introducing the coloring matter ofthe invention, all the commonly used binders are usable. For example,styrene type resins, acrylic type resins, styrene/acrylic type resins,and polyester resins may be mentioned.

To the toner, inorganic fine powder and organic fine particles may beexternally added for the purposes of improving the fluidity, controllingthe electric charge, or other purposes. Silica fine particles or titaniafine particles, surface-treated with a coupling agent containing analkyl group are preferably used. Incidentally, these preferably have anumber average primary particle diameter of 10 to 500 nm, and preferablyare added into the toner in an amount of 0.1 to 20 mass %.

All the release agents which have been conventionally used may be usedas the release agents. Specifically, mention may be made of olefins suchas low-molecular-weight polypropylenes, low-molecular-weightpolyethylenes, and ethylene/propylene copolymers; microcrystalline wax,carnauba wax, sazol wax, paraffin wax, and the like. These are eachpreferably added into the toner in an amount of 1 to 5 mass %.

The charge control agent may be added, if required. They are preferablyachromatic from the viewpoint of color-forming property. Examplesthereof may include those having a quaternary ammonium salt structure ora calyx allene structure.

The carrier to be used may be either an uncoated carrier composed ofonly magnetic material particles of iron, ferrite, or the like, or aresin-coated carrier obtained by coating the surface of a magneticmaterial particle with a resin or the like. The average particlediameter of this carrier is preferably 30 to 150 μm in terms of volumeaverage particle diameter.

The method for forming an image, to which the toner of the invention isapplicable, has no particular restriction. Examples of the method mayinclude a method in which color images are repeatedly formed on aphotosensitive material, and then transferred, to form an image; and amethod in which images formed on a photosensitive material aretransferred to an intermediate transfer material and the likesequentially, then a color image is formed on the intermediate transfermaterial or the like, and then is transferred to an image-forming membersuch as paper, to form a color image.

[Heat Sensitive Recording (Transfer) Material]

The heat sensitive recording material is formed of an ink sheetincluding the coloring matter of the invention coated on a supporttogether with a binder, and an image receiving sheet which fixes thecoloring matter transferred in accordance with a heat energy appliedfrom a thermal head in response to an image recording signal. The inksheet can be formed in the following manner. The compound of theinvention is dissolved in a solvent with a binder. Alternatively, it isdispersed in the form of fine particles in a solvent. As a result, anink solution is prepared, and the ink is coated on a support, andappropriately dried. The amount of the ink to be coated on the supporthas no particular restriction. However, it is preferably 30 to 1000mg/m². As the preferred binder resins, ink solvents, supports, andfurther image receiving sheets, those described in JP-A-7-137466 can bepreferably used.

In order to apply the heat sensitive recording material to a heatsensitive recording material capable of full color image recording,preferably a cyan ink sheet containing a heat diffusible cyan coloringmatter capable of forming a cyan image, a magenta ink sheet containing aheat diffusible magenta coloring matter capable of forming a magentaimage, and a yellow ink sheet containing a heat diffusible yellowcoloring matter capable of forming a yellow image are sequentiallycoated on a support for the formation. Alternatively, if required,another ink sheet containing a black image forming material may befurther formed.

[Color Filter]

As the methods for forming a color filter, there is a method in whichfirst, a pattern is formed with a photoresist, followed by dyeing, or amethod in which as disclosed in JP-A-4-163552, JP-A-4-128703, andJP-A-4-175753, a pattern is formed by a photoresist to which a coloringmatter has been added. As the methods used for introducing the coloringmatter of the invention into a color filter, any of these methods may beused. As the preferred method, mention may be made of the followingmethod for forming a color filter as described in JP-A-4-175753 orJP-A-6-35182. A positive type resist composition containing athermosetting resin, a quinonediazide compound, a crosslinking agent, acolorant, and a solvent is coated on a substrate. Then, it is exposed tolight through a mask to develop the exposed area. As a result, apositive type resist pattern is formed, and the entire surface of thepositive type resist pattern is exposed to light. Then, the positivetype resist pattern after exposure is hardened. Alternatively, accordingto an ordinary method, a black matrix is formed, which can provide a R,G, and B primary color type or Y, M, and C complementary color typecolor filter. Also for the color filter, the amount of the coloringmatter to be used has no particular restriction. However, it ispreferably 0.1 to 50 mass %.

As the thermosetting resin, quinonediazide compound, crosslinking agent,and solvent, for use in this step, and the amounts thereof, thosedescribed in the foregoing patent documents may be preferably used.

EXAMPLES

Below, the invention will be described by way of examples. However, theinvention is by no way limited thereto.

Example 1

As the typical example, a method for synthesizing a coloring matter(DYE-11) will be described.

(1) Synthesis of Compound b:

25.5 g of sodium hydrogen carbonate and 150 mL of ion exchange waterwere heated to 40° C. 25.0 g of cyanuric chloride (product from TokyoChemical Industry Co., Ltd.) was divided into 5 portions and addedthereto every 10 minutes, and stirred for 1 hour. The solution was addeddropwise to a mixed solution (8° C.) of 52.8 mL of hydrazine and 47 mLof ion exchange water so that the internal temperature does not exceed10° C. The internal temperature was increased up to 50° C., and stirringwas carried out for 30 minutes. The precipitated crystal was filtrated,thereby to obtain 23.4 g of compound b (hydrazine derivative: m.p.>300°C.). The yield was 94.7%.

(2) Synthesis of Compound c:

35.0 g of the compound b (hydrazine derivative) was suspended in 420 mLof ethylene glycol, and stirred at an internal temperature of 50° C. 59mL of concentrated hydrochloric acid and subsequently 60.1 g of pivaloylacetonitrile (product from Tokyo Chemical Industry Co., Ltd.) wereadded, and stirred at 50° C. for 10 hours. 95 mL of concentratedhydrochloric acid and 145 mL of methanol were additionally added, andstirring was further carried out for 8 hours. The solution was cooled toroom temperature, and then, the precipitated crystal was filtrated away,thereby to obtain 81.6 g of a compound c (5-aminopyrazole derivative:m.p.=233 to 235° C.). The yield was 94.2%. ¹H-NMR (DMSO-d6), δ value TMSstandard: 1.2 to 1.3 (18H, s))

(3) Synthesis of Compound e:

90.57 g of a compound d (product from Tokyo Chemical Industry Co., Ltd.)was suspended in 500 ml of H₂O, and 130 ml of concentrated hydrochloricacid was poured. Then, the solution was cooled until the internaltemperature became 5° C. or less. Then, 36.23 g of sodium nitrite and 70ml of an aqueous solution were added dropwise thereto at an internaltemperature in the range of 4 to 6° C. Further, stirring was carried outat an internal temperature of 5° C. or less for 30 minutes. Then, 159 gof sodium sulfite and 636 ml of H₂O were poured while keeping theinternal temperature at 20° C. or less. Further, at an internaltemperature of 25° C., 250 ml of concentrated hydrochloric acid waspoured. Subsequently, stirring was carried out at an internaltemperature 90° C. for 1 hour. Then, the internal temperature was cooledto room temperature, followed by filtration, washing with 200 ml ofwater, and air drying. Then, 80.0 g of a compound e was obtained.

(4) Synthesis of Compound f:

To 209 ml of an ethanol suspension of 23.3 g of the compound e, 28 ml oftriethylamine was added dropwise at room temperature. Then, 12.2 g ofethoxy methylene malononitrile (ALDRICH product) was divided and addedthereto. The solution was refluxed for 3 hours, cooled down to roomtemperature, followed by filtration, and washed with 400 ml of isopropylalcohol, and dried. Then, 23.57 g of a compound f was obtained.

(5) Synthesis of DYE-11:

At an internal temperature of 4° C. or less, to 32.4 mL of sulfuricacid, 145.56 mL of acetic acid was poured. Subsequently, with stirringat an internal temperature 7° C. or less, 15.9 mL 40% nitrosyl sulfuricacid (ALDRICH product) was added dropwise thereto.

32.4 g of a compound f was divided and added, and with stirring at aninternal temperature 10° C., stirring was carried out at the sametemperature for 60 minutes. Then, 1.83 g of urea was added into thereaction mixture. To a solution obtained by suspending 18.8 g of thecompound C in 470 ml of methanol, diazonium salt was added dropwise atan internal temperature of less than 0° C. Stirring was carried outstill at the same temperature for 30 minutes. Then, the internaltemperature of the reaction solution was increased up to roomtemperature, followed by filtration, washing with methanol, and washingwith H₂O, resulting in a coarse crystal. Subsequently, the coarsecrystal was suspended in 400 ml of methanol, and the suspension wasstirred under reflux for 1 hour. Then, the suspension was cooled down toroom temperature, followed by filtration, washing with methanol, washingwith water, and washing with methanol. Then, drying was carried out at75° C. overnight. Then, 34.4 g of free acid type crystal of DYE-11 wasobtained. The obtained crystal was prepared into a 10 wt % aq (at 25°C.: pH nearly equal to 8.3: KOH aq preparation). Then, at an internaltemperature of 50° C., IPA was added, and crystallized, followed bycooling, filtration, washing with IPA, and drying. Then, 35 g of DYE-11(potassium salt) was obtained.

λmax=436.4 nm (H₂O), ε: 3.53×10⁴ (dm³.cm/mol)

Example 2

Below, synthesis examples of the coloring matter of the invention willbe shown. Other coloring matters can be synthesized in the same mannerby applying the synthesis method of the coloring matter (DYE-11). Theλmax in H₂O and the δ value of each synthesized coloring matter areshown in Table 1.

TABLE 1 DYE-No. λmax (H₂O) ε (H₂O) DYE-8 444.6 nm 3.76 × 10⁴ DYE-9 442.6nm 3.44 × 10⁴ DYE-11 436.4 nm 3.53 × 10⁴ DYE-12 434.3 nm 3.50 × 10⁴DYE-13 449.0 nm 3.66 × 10⁴ DYE-14 435.0 nm 3.60 × 10⁴ DYE-15 437.0 nm3.54 × 10⁴

Example 3

To the following components, ultrapure water (resistance value 18 MΩ ormore) was added to a total volume of 1 liter. Then, stirring was carriedout for 1 hour while heating at 50 to 60° C. Then, the solution wasvacuum filtrated through a micro filter with an average pore diameter of0.25 μm, thereby to prepare a yellow ink solution Y-101.

[Formulation of Yellow Ink Y-101]

(Solid contents) Yellow dye of the invention (DYE-11) 50 g/l Proxel(manufactured by Avecia) 5 g/l Urea 10 g/l (Liquid components)Triethylene glycol monobutyl ether (DGB) 101 g/l Glycerin (GR) 118 g/lTriethylene glycol (DEG) 95 g/l 2-Pyrrolidone 20 g/l Triethanolamine(TEA) 10 g/l Surfynol 465 (SW) (manufactured by Air Products) 10 g/l

Ink solutions Y-102 to 105 were manufactured in the same manner as withthe preparation of the ink solution Y-101, except that the coloringmatter was changed as shown in Table 2 shown below.

At this step, an ink solution 101 was formed by using a comparativecoloring matter a in Table 2 as an ink solution for comparison.

Comparative Coloring Matter a

When the coloring matter was changed, it was used such that the amountof the coloring matter added is equimolar to that of the ink solutionY-101.

Whereas, as the comparative type of the ink, PM-G800 yellow inkcartridge manufactured by EPSON CORPORATION was used.

Incidentally, in Table 2, “discharge stability”, “light fastnessproperty”, “heat fastness property”, “ozone (gas) resistance”, “metalgloss”, “chromaticity”, and “solution stability” were rated in thefollowing manner. Each ink was charged in the cartridge of yellow ink ofan ink jet printer PM-G800 manufactured by EPSON Corp. For other colorinks, inks of PMG800 were used. For the image receiving sheets, EPSONphoto paper sheets <gloss>, and EPSON photo paper sheets CRISPIA <highgloss> were used. Thereon, yellow monochrome image patterns, and green,red, and gray image patterns were printed with stepwise changingdensities. Thus, the image quality, and the ink discharge property andimage fastness property were evaluated.

For the inks for ink jet of the Examples (ink solutions Y101, 102, 103,104, and 105) and Comparative Examples (ink solutions 101 and PM-G800yellow ink), the following evaluations were carried out. The results areshown in Table 2.

(Evaluation Experiment)

1) For the discharge stability, a cartridge was set in a printer, anddischarge of ink from all the nozzles was checked. Then, 20 A4 sizepaper sheets were outputted, and rated based on the following criteria.

A: No irregular printing from the start of printing till the completion;

B: Output with irregular printing occurs; and

C: Irregular printing occurs from the start of printing till thecompletion

2) As for the image storability of the yellow coloring matter, thefollowing evaluations were carried out using printing samples.

[1] As for the light fastness property, the image density immediatelyafter printing was measured by means of X-rite 310. Then, by means of aweather meter manufactured by Atlas Co., the image was irradiated withxenon light (100000 lx) for 14 days. Then, the image density Cf wasmeasured again to determine the dye residual ratio Cf/Ci×100. Thus, theevaluation was carried out. As for the dye residual ratio, theevaluations were carried out at 3 points with reflection densities of 1,1.5, and 2.

The case where the dye residual ratios at all densities were 80% or morewas rated as A; the case where the ratios at two points were less than80% was rated as B; and the case where the ratios at all the densitieswere less than 80% was rated as C.

[2] As for the heat fastness property, a sample was stored for 7 daysunder the conditions of 80° C. and 60% RH. Then, the densities beforeand after storage were measured by means of X-Rite 310 to determine thedye residual ratio. Thus, the evaluation was carried out. As for the dyeresidual ratio, the evaluations were carried out at 3 points withreflection densities of 1, 1.5, and 2. The case where the dye residualratios at all densities were 95% or more was rated as A; the case wherethe ratios at two points were less than 95% was rated as B; and the casewhere the ratios at all the densities were less than 95% was rated as C.

[3] As for the ozone resistance, a sample was allowed to stand in a boxwith an ozone gas concentration set at 5 ppm for 14 days. Then, theimage densities before and after standing under an ozone gas weremeasured by means of a reflection densitometer (X-Rite 310TR). Thus,evaluation was carried out as the dye residual ratio. Incidentally, themeasurements were carried out at 3 points with the reflection densitiesof 1, 1.5, and 2.0. The ozone gas concentration in the box was set bymeans of an ozone gas monitor (model: OZG-EM-01) manufactured byAPPLICS.

The case where the dye residual ratios at all densities were 80% or morewas rated as A; the case where the ratios at one or two points were lessthan 80% was rated as B; and the case where the ratios at all thedensities were less than 70% was rated as C. Thus, rating was conductedon a scale of three levels.

3) Occurrence or non-occurrence of metal gloss: The yellow, and greenand red solid printed image portions were visually observed by reflectedlight, and evaluated.

4) Chromaticity: A yellow monochrome image pattern with a stepwisechanging density was measured for CIE L*a*b* by Spectro Eye manufacturedby Gretag Macbeth. The a* and the b* at a reflection density of 1.0 areshown in Table below.

5) Solution stability: A 10 mass % aqueous solution of each dye wasallowed to stand at 60° C. for 10 days. Then, the absorbance wasmeasured, and the change ratio with respect to the room temperature (23°C.) is shown in Table below.

TABLE 2 [1] Light [2] Heat [3] Ozone Discharge fastness fastnessfastness Chromaticity Chromaticity Solution Coloring Ink stabilityproperty property property Metal gloss a* b* stability matter No. Y101 AA A A Occurrence −9.7 87.5 99.8 DYE-11 Y102 A A A A Occurrence −8.0 84.899.7 DYE-12 Y103 A A A A Occurrence −13.4 78.9 99.7 DYE-8 Y104 A A A AOccurrence −10.5 80.3 99.8 DYE-9 Y105 A A A A Occurrence −9.9 90.2 99.7DYE-13 101 A B A B Non-Occurrence −6.3 82.1 49.8 Comparative coloringmatter a PM-G800 A C B C Occurrence −7.6 74.8 99.9 —

The results of the table indicate as follows. With the system using theink of the invention, the discharge property and the weatherability areexcellent, and the occurrence of metal gloss is suppressed. The hue asyellow is excellent (a* is minus=less reddish, and b* is large=highcolor saturation), and the solution stability is excellent.

As apparent from the results of Table-2, with the system using the inkof the invention, all the performances are excellent. Particularly, ascompared with Comparative Examples, the image fastness property and theink stability are excellent.

Example 4

The same ink as that manufactured in Example 3 was printed on the photogloss paper “Gasai” manufactured by Fuji Photo Film Co., Ltd., by thesame machine as that in Example 3. Then, the same evaluation as those inExample 3 were carried out. As a result, the same results were obtained.

Example 5

(Manufacturing of Ink Solution D)

2.5 g of the coloring matter of the invention (DYE-19) and 7.04 g ofsodium dioctylsulfosuccinate were dissolved in 4.22 g of the followinghigh boiling point organic solvent (s-2), 5.63 g of the following highboiling point organic solvent (s-11), and 50 ml of ethyl acetate at 70°C. To the resulting solution, 500 ml of deionized water was added withstirring by means of a magnetic stirrer. Thus, an oil-in-water typecoarse particle dispersion was manufactured. Then, the coarse particledispersion was allowed to pass through a Microfluidizer (MICROFLUIDEXINC) under a pressure of 600 bar five times to be finely reduced in sizeof particles. Further, the resulting emulsion was subjected todesolvation by means of a rotary evaporator until there was no odor ofethyl acetate. To the microfine emulsion of a hydrophobic dye thusobtained, 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL465 (AirProducts & Chemical Co.), and 900 ml of deionized water wereadded to manufacture an ink solution D. The ink had a pH of 8.5, aviscosity of 4.1 mPa·S, and a surface tension of 33 mN/m.

(Manufacturing of Ink Solution 103)

An ink solution 103 was manufactured in the same manner as with the inksolution D, except that the coloring matter of the invention of the inksolution D was changed to the equimolar comparative coloring matter ofTable 3 below. The pH, viscosity, and surface tension of the inksolution were the same as those of the ink solution D.

(Image Recording and Evaluation)

For the ink solution D and the comparative ink solution 103, thefollowing evaluations were carried out. The results are shown in Table 3below.

Incidentally, in Table 3, the contents of “tone (λmax)”, “lightresistance”, “ozone (gas) resistance”, “heat resistance”, and “inkstability” are respectively the same as those described in Example 3.

TABLE 3 Coloring Tone Light Ozone Heat Ink Sample matter (λmax)resistance resistance resistance stability D DYE-19 A A A A A 103Comparative B (430 nm) C C A A coloring matter C

Comparative Coloring Matter c

Apparent from Table 3, the ink for ink jet of the invention is excellentin tone, and excellent in light resistance, ozone resistance, heatresistance, and ink stability.

Example 6

The same ink as that manufactured in Example 5 was printed on the inkjet paper photo gloss paper “Gasai” manufactured by Fuji Photo Film Co.,Ltd., by the same machine as that in Example 5. Then, the sameevaluations as those in Example 5 were carried out. As a result, thesame results as those in Example 5 were obtained.

Example 7

3 parts by mass of the coloring matter of the invention (DYE-20) and 100parts by mass of a resin for toner [styrene-acrylic acid estercopolymer; trade name HIMER TB-1000F (manufactured by Sanyo ChemicalIndustries, Ltd.)] were mixed and ground in a ball mill. Then, themixture was heated to 150° C. to be molten and mixed. After cooling, themixture was coarsely crushed using a hammer mill, and then, finelypulverized by a pulverizer of an air jet system. The resulting particleswere further classified, and 1 to 20 micro was selected, resulting in atoner. To 10 parts of the toner, 900 parts by mass of carrier ironpowder (trade name EFV250/400; manufactured by Nippon Iron Powder) wasuniformly mixed, resulting in a developer. Similarly, each sample wasprepared in the same manner, except that the coloring matter shown inTable 4 was used in an amount of 3 parts by mass. By the use of thesedevelopers, copying was carried out by means of a dry ordinary paperelectrophotographic copier [trade name NP-5000; manufactured by CANON,Corp.].

Reflected images (images on paper) and transmitted images (OHP images)were formed on paper and OHP sheets, respectively, with a developerusing the color toner of the invention in accordance with the foregoingimage forming method, and the evaluation tests were conducted in thefollowing manner. Incidentally, the amount of the toner deposited wasevaluated in the range of 0.7±0.05 (mg/cm²).

The resulting images were evaluated for the hue and the light fastnessproperty. The hue was visually rated on a scale of three levels of best,good, and bad. The evaluation results are shown in Table 4. In Table 4below, AA denotes that the hue is best; BB denotes that the hue is good;and CC denotes that the hue is bad. The light fastness property wasevaluated in the following manner. The image density Ci immediatelyafter recording was measured, and thereafter, the image was irradiatedwith xenon light (85,000 lux) by means of a weather meter (Atlas C.165), for 5 days. Then, the image density Cf was measured again, and thecoloring matter residual ratio ({Ci−Cf/Ci}×100%) was calculated from thedifference in image density between before and after xenon lightirradiation. The image density was measured by means of a reflectiondensitometer (X-Rite 310TR). The evaluation results are shown in Table 4below. In Table 4, the case where the coloring matter residual ratio was90% or more is indicated with AA; the case of 90 to 80%, BB; and thecase of less than 80%, CC.

The transparency of the OHP image was evaluated in the following manner.By means of a “330 model autographic spectrophotometer” manufactured byHitachi Ltd., the visible spectral transmittance of the image wasmeasured with the OHP sheet having no toner carried thereon as areference. The spectral transmittance at 650 nm was determined, andtaken as the scale for the transparency of the OHP sheet. The case ofthe spectral transmittance of 80% or more is indicated with AA; 70 to80%, BB; and less than 70%, CC. The results up to this point are shownin Table 4.

TABLE 4 Light fastness DYE-No. Hue property Transparency InventionDYE-20 AA AA AA Comparative C.I. Solvent. BB BB BB Example Yellow 162

Apparent from Table 4, use of the color toner of the invention providesfaithful color reproduction and high OHP quality. For this reason, thecolor toner of the invention is suitable for use as a full color toner.Further, it is good in light resistance, which can provide imagesstorable over a long period.

Example 8

<Formation of Heat Transfer Coloring Matter Donating Material>

As a support, a polyethylene terephthalate film subjected to a heatresistant slip treatment on the back side, and with a thickness of 6 μm(manufactured by TEIJIN Limited.) was used. Thus, on the surface of thefilm, a coating composition for a heat transfer coloring matter donatinglayer with the following composition was coated by means of wire barcoating and formed so that the thickness upon drying was 1.5 μm. Thus, aheat transfer coloring matter donating material (5-1) was formed.

Coating Composition for Heat Transfer Coloring Matter Donating Layer:

Coloring matter (DYE-20) 10 millimol Polyvinyl butyral resin (DenkaButyral 5000-A 3 g manufactured by Denki Kagaku) Toluene 40 ml Methylethyl ketone 40 ml Polyisocyanate (Takenate D110N manufactured by 0.2 mlTakeda Pharmaceutical Company Limited.)

Then, a heat transfer coloring matter donating material of the inventionand a heat transfer coloring matter donating material for comparison(5-2) were formed in the same manner as described above, except that thecoloring matter (DYE-20) was changed to the comparative coloring matterdescribed in Table 5.

(Formation of Heat Transfer Image Receiving Material>

As a support, a synthetic paper sheet with a thickness of 150 μm(YUPO-FPG150, manufactured by Oji Yuka) was used. Thus, on the surface,the following composition was coated by means of wire bar coating sothat the thickness upon drying was 8 μm. Thus, a heat transfer imagereceiving material was formed. Drying was carried out in an oven at atemperature of 100° C. for 30 minutes after temporary drying by a dryer.

Coating Composition of Image Receiving Layer:

Polyester resin (VYLON-280 manufactured by Toyobo 22 g Co., Ltd.)Polyisocyanate (KP-90 manufactured by Dainippon 4 g Ink & Chemicals,Inc.) Amino-modified silicone oil (KF-857 manufactured 0.5 g byShin-Etsu Silicone) Methyl ethyl ketone 85 ml Toluene 85 mlCyclohexanone 15 ml

The heat transfer coloring matter donating materials (5-1) and (5-2) andthe heat transfer image receiving material obtained in the foregoingmanner were stacked one on another in such a manner that the heattransfer coloring matter donating layers and the image receiving layerwere in contact with one another. Printing was carried out using athermal head from the support side of the heat transfer coloring matterdonating material under conditions of a thermal head output of 0.25W/dot, a pulse width of 0.15 to 15 msec, and a dot density of 6 dots/mm.Thus, a coloring matter of yellow was dyed in the form of an image inthe image receiving layer of the image receiving material. The maximumcolor optical density of each resulting image is shown in Table 5. Withthe heat transfer coloring matter donating material (5-1) of theinvention, it was possible to obtain clear image recording with notransfer blur. Then, each pre-recorded heat transfer image receivingmaterial obtained in the foregoing manner was irradiated with a Xe light(17,000 lux) for 5 days to examine the light stability of the coloredimage. The status A reflection density after irradiation of the portionindicating a status A reflection density of 1.0 was measured. Thestability was evaluated in terms of the residual ratio (percentage)relative to the reflection density of 1.0 before irradiation. Theresults are shown in Table 5.

TABLE 5 Heat transfer Light coloring matter Maximum fastness donatingmaterial DYE-No. density property Remark 5-1 DYE-20 1.9 95 Invention 5-2Comparative 1.8 52 Comparative coloring matter d

Comparative Coloring Matter d

As described above, the coloring matter of the invention was excellentin light fastness property as compared with the comparative dye.Further, the hue was also vivid.

Example 9

The color filter was manufactured in the following manner. Onto asilicon wafer, a positive type resist composition containing athermosetting resin, a quinonediazide compound, a crosslinking agent, acoloring matter, and a solvent was spin coated. The solvent wasevaporated by heating, followed by exposure to light through a mask, todecompose the quinonediazide compound. If required, after heating,development was carried out to obtain a mosaic pattern. The exposure tolight was carried out by means of an i-ray exposure stepper HITACHILD-5010-i (NA=0.40) manufactured by Hitachi Ltd. Whereas, the developerused was SOPD or SOPD-B manufactured by Sumitomo Chemical Co., Ltd.

<Preparation of Positive Type Resist Composition>

3.4 parts by mass of a cresol novolak resin (polystyrene equivalentmolecular weight 4300) resulting from a m-cresol/p-cresol/formaldehyde(reaction mole ratio=5/5/7.5) mixture, 1.8 parts by mass ofo-naphthoquinonediazide-5-sulfonic acid ester (an average of twohydroxyl groups have been esterified) manufactured by using a phenolcompound represented by the following formula, 0.8 part by mass ofhexamethoxymethylolated melamine, 20 parts by mass of ethyl lactate, and1 part by mass of the coloring matter of the invention (DYE-20) shown inTable 6 were mixed, resulting in a positive type resist composition.

<Preparation of Color Filter>

The resulting positive type resist composition was spin coated onto asilicon wafer. Then, the solvent was evaporated. The silicon wafer wasexposed to light, and then heated at 100° C. Then, the exposed portionwas removed by the alkali development to obtain a positive type coloredpattern having a 0.8-μm resolution. This was entirely exposed to light,and then, heated at 150° C. for 15 minutes, resulting in a cyancomplementary color type color filter.

Comparative Example

In place of the yellow coloring matter of the invention used in theexamples, 1 part by mass of Oleosol yellow 2G manufactured by SumitomoChemical Co., Ltd., was mixed, resulting in a positive type resistcomposition. The resulting positive type resist composition was spincoated onto a silicon wafer. Then, the solvent was evaporated. Thesilicon wafer was exposed to light, and then subjected to alkalidevelopment, resulting in a positive type colored pattern having a 1-μmresolution. This was entirely exposed to light, and then, heated at 150°C. for 10 minutes, resulting in a yellow color filter.

<Evaluation>

The transmission spectrum of the resulting yellow color filter wasmeasured, and the cutting on the short wavelength side or the longwavelength side of the spectrum important for color reproduction wasrelatively evaluated. AA denotes good; BB denotes somewhat acceptablelevel; and CC, unacceptable level. Further, the filter was irradiatedwith xenon light (85000 1×) by means of a weather meter (Atlas C. 165)for 7 days. Then, the image densities before and after xenon irradiationwere measured, and evaluation was carried out based on the coloringmatter residual ratio.

TABLE 6 Absorption Light fastness Dye-No. characteristics propertyInvention DYE-20 AA 98% Comparative Oleosol yellow 2G BB 59% Example

The coloring matter of the invention exhibits a sharper cutting on theshort wavelength side or on the long wavelength side of the spectrum,and is excellent in color reproducibility as compared with ComparativeExample. Further, it has been shown that the coloring matter of theinvention is superior in light fastness property to the comparativecompound.

INDUSTRIAL APPLICABILITY

The coloring matters of the invention are preferably used for variouscoloring compositions in ink for printing of ink jet or the like, an inksheet in a heat sensitive recording material, a color toner forelectrophotography, displays such as LCD and PDP, image pick-up devicessuch as CCDs, and dying solutions for dying of various fibers.

Although the invention has been described in detail, and with referenceto specific embodiments thereof, it will be apparent to those skilled inthe art that various changes and modifications can be made withoutdeparting from the spirit and the scope of the invention.

This application is based on Japanese Patent Application (JapanesePatent Application No. 2005-030466) filed on Feb. 7, 2005, and JapanesePatent Application (Japanese Patent Application No. 2005-226768) filedon Aug. 4, 2005, the contents of which are incorporated herein byreference.

1. A compound represented by the following formula (7), or a salt or ahydrate thereof:

wherein in the formula, R₃ and R₄ each independently represents amonovalent group; P₁ and P₂ each independently represents a hydrogenatom an alkyloxy group, an aryloxy group, an alkylthio group or anarylthio group; and M represents a hydrogen atom or a cation.
 2. Thecompound according to claim 1, wherein P₁ and P₂ are a hydrogen atom.